ETHYLENE-a-OLEFIN COPOLYMER AND MOLDED ARTICLE

ABSTRACT

An ethylene-α-olefin copolymer wherein the copolymer has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, the density (d) is 860 to 950 kg/m 3 , the melt flow rate (MFR) is 1 to 100 g/10 min, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 to 30, the ratio (Mz/Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 2 to 5, the swell ratio (SR) is 1.8 or more, and the characteristic relaxation time (τ) obtained by linear viscoelasticity measurement is 0.01 to 10 seconds.

TECHNICAL FIELD

The present invention relates to an ethylene-α-olefin copolymer and amolded article obtained by extrusion molding of the ethylene-α-olefincopolymer.

BACKGROUND ART

Ethylene-α-olefin copolymers are molded into a film, sheet, bottle orthe like by various molding methods, and subjected to variousapplications such as a food packaging material and the like.

Among ethylene-α-olefin copolymers, copolymers polymerized using ametallocene catalyst are known to have excellent mechanical strengthssuch as impact strength, tensile strength and the like. Thus, thesecopolymers have been investigated to be utilized in various applicationssince weight reduction and cost reduction of a molded article can beexpected while maintaining mechanical strengths, by rendering the moldedarticle thinner. However, an ethylene-α-olefin copolymer polymerizedusing a conventional metallocene catalyst shows high extrusion load inextrusion processing, and manifests small melt tension and swell ratio,thus, molding processability thereof is not sufficient and itsutilization is limited.

In contrast, recently, a novel metallocene catalyst has beeninvestigated, and an ethylene-α-olefin copolymer having improved moldingprocessability polymerized using this catalyst has been suggested. Forexample, JP-A No. 2003-96125 describes an ethylene-α-olefin copolymerpolymerized using a metallocene catalyst composed of a transition metalcompound having a ligand prepared by connecting of two groups having acyclopentadiene type anion skeleton via a crosslinking group, atransition metal compound having two groups having a substitutedcyclopentadiene type anion skeleton not mutually connected, and acocatalyst component for activation. JP-A No. 2004-149761 describes anethylene-α-olefin copolymer polymerized using a metallocene catalystcomposed of racemic-ethylenebis(1-indenyl)zirconium diphenoxide;triisobutylaluminum; and a cocatalyst component prepared by contactingof silica, hexamethyldisilazane, diethylzinc, pentafluorophenol andwater. JP-A No. 2006-233206 describes an ethylene-α-olefin copolymerpolymerized using a metallocene catalyst combining a transition metalcompound having a ligand prepared by connecting of two groups having acyclopentadiene type anion skeleton via a crosslinking group with atransition metal compound having a ligand prepared by connecting a grouphaving a cyclopentadiene type anion skeleton and a group having afluorenyl type anion skeleton via a crosslinking group; and a carrierprepared by supporting methylalumoxane as a cocatalyst on porous silica.

However, the ethylene-α-olefin copolymers described in JP-A No.2003-96125 and JP-A No. 2004-149761 are not yet sufficientlysatisfactory in extrusion load and swell ratio in molding processing,and the ethylene-α-olefin copolymer described in JP-A No. 2006-233206has still insufficient swell ratio, and additionally, the moltenethylene-α-olefin copolymer molecular chain has a long relaxation time,thus, the appearance of a molded article obtained by molding and thetaking-up property in molding are not yet sufficiently satisfactory.

DISCLOSURE OF THE INVENTION

Under such states, a problem to be solved by the present invention is toprovide an ethylene-α-olefin copolymer excellent in extrusion load,swell ratio and mechanical strength, and showing a sufficiently shortrelaxation time of the molecular chain in molten condition, and a moldedarticle obtained by extrusion molding of this copolymer. The presentinventors have intensively studied to solve the problem, leadingresultantly to completion of the present invention.

The present invention relates, in a first aspect, to anethylene-α-olefin copolymer wherein the copolymer has a monomer unitbased on ethylene and a monomer unit based on an α-olefin having 3 to 20carbon atoms, the density (d) is 860 to 950 kg/m³, the melt flow rate(MFR) is 1 to 100 g/10 min, the ratio (Mw/Mn) of the weight averagemolecular weight (Mw) to the number average molecular weight (Mn) is 4to 30, the ratio (Mz/Mw) of the Z average molecular weight (Mz) to theweight average molecular weight (Mw) is 2 to 5, the swell ratio (SR) is1.8 or more, and the characteristic relaxation time (τ) obtained bylinear viscoelasticity measurement is 0.01 to 10 seconds.

The present invention relates, in a second aspect, to a molded articleobtained by extrusion molding of the above-described ethylene-α-olefincopolymer.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

The ethylene-α-olefin copolymer of the present invention is anethylene-α-olefin copolymer containing a monomer unit based on ethyleneand a monomer unit based on an α-olefin having 3 to 20 carbon atoms. Theα-olefin includes propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene,4-methyl-1-hexene and the like, and these may be used singly or incombination of two or more. The α-olefin includes preferably 1-butene,1-hexene, 4-methyl-1-pentene and 1-octene.

The ethylene-α-olefin copolymer of the present invention may alsocontain a monomer unit based on other monomer in a range notdeteriorating the effect of the present invention, in addition to theabove-described monomer unit based on ethylene and the above-describedmonomer unit based on an α-olefin having 3 to 20 carbon atoms. Examplesof the other monomer include conjugated dienes (for example, butadieneand isoprene), non-conjugated dienes (for example, 1,4-pentadiene),acrylic acid, acrylates (for example, methyl acrylate and ethylacrylate), methacrylic acid, methacrylates (for example, methylmethacrylate and ethyl methacrylate), vinyl acetate and the like.

The content of the monomer unit based on ethylene in theethylene-α-olefin copolymer of the present invention is usually 50 to99.5% by weight with respect to the total weight (100% by weight) of theethylene-α-olefin copolymer. The content of the monomer unit based on anα-olefin is usually 0.5 to 50% by weight with respect to the totalweight (100% by weight) of the ethylene-α-olefin copolymer.

The ethylene-α-olefin copolymer of the present invention is preferably acopolymer having a monomer unit based on ethylene and a monomer unitbased on an α-olefin having 4 to 20 carbon atoms, more preferably acopolymer having a monomer unit based on ethylene and a monomer unitbased on an α-olefin having 5 to 20 carbon atoms, and further preferablya copolymer having a monomer unit based on ethylene and a monomer unitbased on an α-olefin having 6 to 8 carbon atoms.

Examples of the ethylene-α-olefin copolymer of the present inventioninclude an ethylene-1-butene copolymer, ethylene-1-hexene copolymer,ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer,ethylene-1-butene-1-hexene copolymer,ethylene-1-butene-4-methyl-1-pentene copolymer,ethylene-1-butene-1-octene copolymer, ethylene-1-hexene-1-octenecopolymer and the like, preferably an ethylene-1-hexene copolymer,ethylene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-hexenecopolymer, ethylene-1-butene-1-octene copolymer andethylene-1-hexene-1-octene copolymer.

The density of the ethylene-α-olefin copolymer of the present invention(hereinafter, referred to as “d” in some cases) is 860 to 950 kg/m³.From the standpoint of enhancing the mechanical strength of theresultant molded article, the density is preferably 940 kg/m³ or less,more preferably 935 kg/m³ or less, and further preferably 930 kg/m³ orless. From the standpoint of enhancing the rigidity of the resultantmolded article, the density is preferably 870 kg/m³ or more, morepreferably 880 kg/m³ or more, further preferably 890 kg/m³ or more, andparticularly preferably 900 kg/m³ or more. The density is measuredaccording a method defined in method A in JIS K7112-1980, afterperforming annealing described in JIS K6760-1995. The density of theethylene-α-olefin copolymer can be altered by the content of the monomerunit based on ethylene in the ethylene-α-olefin copolymer.

The melt flow rate of the ethylene-α-olefin copolymer of the presentinvention (hereinafter, referred to as “MFR” in some cases) is usually 1to 100 g/10 min. The melt flow rate is preferably 1.5 g/10 min or more,from the standpoint of reducing the extrusion load in moldingprocessing. From the standpoint of increasing the mechanical strength ofthe resultant molded article, the melt flow rate is preferably 50 g/10min or less, more preferably 20 g/10 min or less, and preferably 10 g/10min or less. The melt flow rate is a value measured by method A underconditions of a temperature of 190° C. and a load of 21.18 N in a methoddefined in JIS K7210-1995. The melt flow rate of the ethylene-α-olefincopolymer can be altered, for example, by the hydrogen concentration orpolymerization temperature in a production method to be described later,and when the hydrogen concentration or polymerization temperature israised, the melt flow rate of the ethylene-α-olefin copolymer increases.

The ratio (hereinafter, referred to as “Mw/Mn” in some cases) of theweight average molecular weight (hereinafter, referred to as “Mw” insome cases) to the number average molecular weight (hereinafter,referred to as “Mn” in some cases) is 4 to 30, and the ratio(hereinafter, referred to as “Mz/Mw” in some cases) of the Z averagemolecular weight (hereinafter, referred to as “Mz” in some cases) to theweight average molecular weight (Mw) is 2 to 5, in the ethylene-α-olefincopolymer of the present invention. When Mw/Mn is too small, theextrusion load in molding processing becomes higher in some cases. Mw/Mnis preferably 4.5 or more, more preferably 5.5 or more, and furtherpreferably 6 or more. When Mz/Mw is too large, the relaxation time of amolecular chain of a polymer in molten condition becomes longer in somecases. Mz/Mw is preferably 4.5 or less, more preferably 4 or less. WhenMw/Mn is too large or when Mz/Mw is too small, the mechanical strengthof the resultant molded article becomes lower in some cases. Mw/Mn ispreferably 25 or less, more preferably 20 or less, further preferably 15or less, and particularly preferably 12 or less. Mz/Mw is preferably 2.5or more. The Mw/Mn and the Mz/Mw are obtained by measuring the numberaverage molecular weight (Mn), the weight average molecular weight (Mw)and the Z average molecular weight (Mz) by a gel permeationchromatograph (GPC) method and dividing Mw by Mn and dividing Mz by Mw.The Mw/Mn can be altered, for example, by the hydrogen concentration orpolymerization temperature in a production method to be described later,and when the hydrogen concentration or polymerization temperature israised, the Mw/Mn of the ethylene-α-olefin copolymer increases. TheMz/Mw can be altered, for example, by the use ratio of a transitionmetal compound (A1) and a transition metal compound (A2) in a productionmethod to be described later, and when the use ratio of a transitionmetal compound (A2) is lowered, the Mz/Mw of the ethylene-α-olefincopolymer becomes smaller.

Mz/Mw represents the molecular weight distribution of higher molecularweight components, and smaller Mz/Mw as compared with Mw/Mn means thatthe molecular weight distribution of higher molecular weight componentsis narrow and the ratio of very higher molecular weight components, thatis, the ratio of components showing a very long relaxation time issmall, and larger Mz/Mw as compared with Mw/Mn means that the molecularweight distribution of higher molecular weight components is wide andthe ratio of very higher molecular weight components, that is, the ratioof components showing a very long relaxation time is high. From thestandpoint of reducing the extrusion load and from the standpoint ofshortening the relaxation time, (Mw/Mn)—(Mz/Mw) is preferably 1 or more,and more preferably, (Mw/Mn)—(Mz/Mw) is 2 or more. (Mw/Mn)—(Mz/Mw) canbe altered, for example, by the use ratio of a transition metal compound(A1) and a transition metal compound (A2), and when the use ratio of atransition metal compound (A2) is increased, (Mw/Mn)—(Mz/Mw) of theethylene-α-olefin copolymer becomes larger. (Mw/Mn)—(Mz/Mw) can beincreased also by performing prepolymerization.

The swell ratio (hereinafter, referred to as “SR” in some cases) of theethylene-α-olefin copolymer of the present invention is 1.8 or more.When the swell ratio is too small, neck-in becomes larger in flat diefilm molding, in some cases. The swell ratio is preferably 1.85 or more,more preferably 1.9 or more, and further preferably 2.0 or more. Theswell ratio is preferably 2.5 or less, from the standpoint of enhancingthe taking-up property in extrusion molding. A strand of anethylene-α-olefin copolymer extruded with a length of about 15 to 20 mmfrom an orifice under conditions of a temperature of 190° C. and a loadof 21.18 N, in measuring the melt flow rate (MFR), is cooled in air, andthe diameter D (unit: mm) of the resultant solid strand is measured at aposition about 5 mm from the end at the extrusion upstream side and thediameter D is divided by the orifice diameter: 2.095 mm (D₀), to givethe value of the swell ratio. The swell ratio can be altered, forexample, by the hydrogen concentration and the ethylene pressure or theelectron donating compound concentration, in polymerization, in aproduction method to be described later, and when the hydrogenconcentration is raised and the ethylene pressure is lowered, the swellratio of the ethylene-α-olefin copolymer increases. In addition, theswell ratio can be controlled by performing prepolymerization inpolymerization, and the like.

The number of branches having 5 or more carbon atoms (hereinafter,referred to as “N_(LCB)” in some cases) of the ethylene-α-olefincopolymer of the present invention is preferably 0.1/1000 C or more,more preferably 0.12/1000 C or more, from the standpoint of furtherreducing the extrusion load in molding processing. From the standpointof enhancing the mechanical strength of the resultant molded article, itis preferably 1/1000 C or less, more preferably 0.7/1000 C or less. TheN_(LCB) can be altered, for example, by the concentration of an electrondonating compound or the use ratio of a transition metal compound (A1)and a transition metal compound (A2), in a production method to bedescribed later. The N_(LCB) can be controlled also by performingprepolymerization.

N_(LCB) is obtained by calculating the area of a peak derived from amethine carbon to which branches having 5 or more carbon atoms areconnected, from a ¹³C-NMR spectrum measured by a carbon nuclear magneticresonance (¹³C-NMR) method, the sum of the areas of all peaks observedbetween 5 to 50 ppm being 1000. A peak derived from a methine carbon towhich branches having 7 or more carbon atoms are connected is observedaround 38.2 ppm (see: academic literature “Macromolecules”, (USA),American Chemical Society, 1999, vol. 32, p. 3817-3819). Since theposition of the peak derived from a methine carbon to which brancheshaving 5 or more carbon atoms are connected shifts depending on ameasuring apparatus and measuring conditions, the position is usuallydetermined by measuring a sample for every measuring apparatus andmeasuring conditions. For spectrum analysis, it is preferable to use anegative exponential function as a window function.

The characteristic relaxation time (hereinafter, referred to as “τ” insome cases) of the ethylene-α-olefin copolymer of the present inventionis 0.01 to 10 seconds, from the standpoint of enhancing the taking-upproperty in molding and the appearance of a molded article. Thecharacteristic relaxation time is a numerical value showing the lengthof a long chain branch in the ethylene-α-olefin copolymer, and when thelong chain branch is shorter, the characteristic relaxation time is asmaller value and when the long chain branch is longer, thecharacteristic relaxation time is a larger value. The characteristicrelaxation time is preferably 0.1 second or more. The characteristicrelaxation time is preferably 5 seconds or less. The characteristicrelaxation time can be altered, for example, by polymerizationconditions such as the hydrogen concentration, ethylene pressure and thelike, and the use ratio of a transition metal compound (A1) and atransition metal compound (A2), and the characteristic relaxation timeof the ethylene-α-olefin copolymer can be made shorter by decreasing theuse ratio of a transition metal compound (A2).

The characteristic relaxation time is a numerical value calculated froma master curve showing the dependency of the melt complex viscosity(unit: Pa·sec) at 190° C. on the angular frequency (unit: rad/sec), madebased on the time-temperature superposition principle. Specifically,melt complex viscosity-angular frequency curves (unit of melt complexviscosity is Pa·sec, unit of angular frequency is rad/sec) of theethylene-α-olefin copolymer at respective temperatures (T, unit: ° C.)of 130° C., 150° C., 170° C. and 190° C. are superposed on a meltcomplex viscosity-angular frequency curve at 190° C. to make a mastercurve, based on the time-temperature superposition principle, and theresultant master curve is approximated according to the followingformula (I), to give a calculated value of the characteristic relaxationtime.

η=η₀/[1+(τ×ω)^(n)]  (I)

η: melt complex viscosity (unit: Pa·sec)

ω: angular frequency (unit: rad/sec)

τ: characteristic relaxation time (unit: sec)

η_(c): constant determined for every ethylene-α-olefin copolymer (unit:Pa·sec)

n: constant determined for every ethylene-α-olefin copolymer

For the above-described calculation, a commercially availablecalculation software may be used, and the calculation software includesRhios V.4.4.4 available from Rheometrics, and the like.

Measurement of a melt complex viscosity-angular frequency curve iscarried out using a viscoelasticity measuring apparatus (for example,Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics,and the like), usually under conditions of geometry: parallel plate,plate diameter: 25 mm, plate interval: 1.5 to 2 mm, strain: 5% andangular frequency: 0.1 to 100 rad/second. The measurement is carried outunder a nitrogen atmosphere, and it is preferable to previously compounda suitable amount (for example, 1000 ppm) of an antioxidant into ameasurement sample.

It is preferable that g* defined by the following formula (II) of theethylene-α-olefin copolymer of the present invention is 0.76 to 0.95(see the following literature for g*: Developments in PolymerCharacterisation-4, J. V. Dawkins,. Ed.,. Applied Science, London,.1983, Chapter. I,. “Characterization. of. Long Chain Branching inPolymers,” written by Th. G. Scholte).

g*=[η]/([η]_(GPC) ×g _(SCB)*)   (II)

[wherein, [η]] represents the limiting viscosity (unit: dl/g) of theethylene-α-olefin copolymer, and defined by the following formula(II-I). It shall be defined by the following formula (II-II). g_(SCB)*is defined by the following formula (II-III).

[η]=23.3×log (ηrel)   (II-I)

(wherein, ηrel represents relative viscosity of the ethylene-α-olefincopolymer)

[η]_(GPC)=0.00046×Mv^(0.725)   (II-II)

(wherein, Mv represents the viscosity average molecular weight of theethylene-α-olefin copolymer)

g _(SCB)* (1-A)^(1.725)   (II-III)

(wherein, A can be determined directly by measurement of the content ofshort chain branches in the ethylene-α-olefin copolymer)].

[η]_(GPC) represents the limiting viscosity (unit: dl/g) of a polymerwhich is hypothesized to have the same molecular weight distribution asthat of the ethylene-α-olefin copolymer and to have a linear molecularchain.

g_(SCB)* represents contribution to g* generated by introduction ofshort chain branches into the ethylene-α-olefin copolymer.

As the formula (II-II), a formula described in L. H. Tung, Journal ofPolymer Science, 36, 130 (1959) p. 287-294 is used.

For the relative viscosity (ηrel) of the ethylene-α-olefin copolymer,100 mg of an olefin polymer is dissolved at 135° C. in 100 ml oftetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as athermal degradation inhibitor to prepare a sample solution, and therelative viscosity is calculated from the fall time of theabove-described sample solution and the fall time of a blank solutioncomposed of tetralin containing only 0.5% by weight of BHT as a thermaldegradation inhibitor obtained by using a Ubbelohde type viscometer.

The viscosity average molecular weight (Mv) of the ethylene-α-olefincopolymer is defined by the following formula (II-IV):

$\begin{matrix}{M_{V} = \left( \frac{\sum\limits_{\mu = 1}^{\infty}{M_{\mu}^{a + 1}n_{\mu}}}{\sum\limits_{\mu = 1}^{\infty}{M_{\mu}n_{\mu}}} \right)^{\frac{1}{a}}} & \left( {{II} - {IV}} \right)\end{matrix}$

wherein a=0.725.

A in the formula (II-III) is estimated asA=((12×n+2n+1)×y)/((1000−2y−2)×14+(y+2)×15+y×13) wherein the number ofbranch carbons in short chain branches is represented by n (for example,n=2 in the case of use of butene as an α-olefin, n=4 in the case of useof hexene as an α-olefin) and the number of short chain branches per1000 carbon atoms measured by NMR or infrared spectrometry isrepresented by y.

g* is an index representing the degree of shrinkage of molecules in asolution ascribable to long chain branches, and when the content of longchain branches per molecular chain is large, shrinkage of the molecularchain increases and g* decreases. g* of the ethylene-α-olefin copolymeris preferably 0.95 or less, more preferably 0.85 or less, from thestandpoint of decreasing extrusion load. When g* is large, extrusionload cannot be decreased sufficiently since long chain branches are notcontained sufficiently. g* of the ethylene-α-olefin copolymer ispreferably 0.76 or more from the standpoint of improvement in mechanicalstrength and shortening of the relaxation time. When g* is too small,spreading of molecular chains when a crystal is formed is too small,thus, the generation probability of a tie molecule lowers, strengthdecreases, and in addition, due to a long chain branched structure, therelaxation time of a molecular chain becomes too long, and theappearance of a molded article deteriorates. g* can be controlled, forexample, by performing prepolymerization.

The flow activation energy (hereinafter, referred to as “Ea” in somecases) of the ethylene-α-olefin copolymer of the present invention ispreferably 50 kJ/mol or more, more preferably 60 kJ/mol or more, fromthe standpoint of further reducing the extrusion load in moldingprocessing. The flow activation energy is preferably 150 kJ/mol or less,more preferably 130 kJ/mol or less, further preferably 110 kJ/mol orless, and most preferably 100 kJ/mol, from the standpoint of enhancingthe taking-up property in extrusion molding. The flow activation energycan be altered, for example, by the use ratio of a transition metalcompound (A1) and a transition metal compound (A2) in a productionmethod to be described later, and when the use ratio of a transitionmetal compound (A2) is enhanced, Ea of the ethylene-α-olefin copolymerincreases.

The flow activation energy (Ea) is a numerical value calculatedaccording to an Arrhenius type equation from a shift factor (a_(T)) inmaking a master curve showing the dependency of melt complex viscosity(unit: Pa·sec) at 190° C. on angular frequency (unit: rad/sec), based onthe time-temperature superposition principle, and is a value obtained bya method described below. That is, melt complex viscosity-angularfrequency curves (unit of melt complex viscosity is Pa·sec, unit ofangular frequency is rad/sec) of the ethylene-α-olefin copolymer atrespective temperatures (T, unit: ° C.) of 130° C., 150° C., 170° C. and190° C. are superposed on a melt complex viscosity-angular frequencycurve of the ethylenic copolymer at 190° C., for each melt complexviscosity-angular frequency curve at each temperature (T), based on thetime-temperature superposition theory, thereby obtaining shift factors(a_(T)) at respective temperatures (T), and a primary approximationformula (the following formula (III)) of [ln(a_(T))] and [1/(T+273.16)]is calculated by a least square method from respective temperatures (T)and shift factors (a_(T)) at respective temperatures (T). Then, Ea isobtained from the inclination m of the primary formula and the followingformula (IV).

In (a _(T))=m(1/(T+273.16))+n   (III)

Ea=10.008314×m|  (IV)

a_(T) : shift factor

Ea: flow activation energy (unit: kJ/mol)

T: temperature (unit: ° C.)

In the above-described calculation, a commercially available calculationsoftware may be used, and the commercially available calculationsoftware includes Rhios V.4.4.4 available from Rheometrics, and thelike.

The shift factor (a_(T)) is move amount when melt complexviscosity-angular frequency double logarithm curves at respectivetemperatures (T) are moved to the log(Y)=−log(X) axis direction (here, Yaxis represents melt complex viscosity, X axis represents angularfrequency) and superposed on a melt complex viscosity-angular frequencycurve at 190° C., and in this superposition, for the melt complexviscosity-angular frequency double logarithm curves at respectivetemperatures (T), the angular frequency is moved by a_(T)-fold and themelt complex viscosity is moved by 1/a_(T)-fold, for each curve. Thecorrelation coefficient in obtaining the formula (I) by a least squaremethod from values at four points of 130° C., 150° C., 170° C. and 190°C. is usually 0.99 or more.

Measurement of the melt complex viscosity-angular frequency curve iscarried out using a viscoelasticity measuring apparatus (for example,Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics,and the like), usually under conditions of geometry: parallel plate,plate diameter: 25 mm, plate interval: 1.5 to 2 mm, strain: 5% andangular frequency: 0.1 to 100 rad/second. The measurement is carried outunder a nitrogen atmosphere, and it is preferable to previously compounda suitable amount (for example, 1000 ppm) of an antioxidant into ameasurement sample.

As the method of producing the ethylene-α-olefin copolymer of thepresent invention, there is mentioned a method of copolymerizingethylene and an α-olefin having 3 to 20 carbon atoms in the presence ofa polymerization catalyst formed by contacting a transition metalcompound (A1) of the following general formula (1), a transition metalcompound (A2) of the following general formula (3) and a cocatalystcomponent (B) described later, the transition metal compound (A1) andthe transition metal compound (A2) are being brought into contact at amolar ratio ((A1)/(A2)) of 1 to 30. (A1)/(A2) is preferably 5 or more,more preferably 10 or more, from the standpoint of shortening therelaxation time of a molecular chain of the ethylene-α-olefin copolymerin molten state and enhancing mechanical strength. (A1)/(A2) ispreferably 20 or less, from the standpoint of enhancing SR.

[wherein, M¹ represents a group IV transition metal atom in the periodictable of the elements, X¹ and R¹ represent each independently a hydrogenatom, a halogen atom, an optionally substituted hydrocarbyl group having1 to 20 carbon atoms, an optionally substituted hydrocarbyloxy grouphaving 1 to 20 carbon atoms, a substituted silyl group having 1 to 20carbon atoms or a substituted amino group having 1 to 20 carbon atoms,and a plurality of X¹ may be mutually the same or different, a pluralityof R¹ may be mutually the same or different, and Q¹ represents acrosslinking group of the following general formula (2).

(wherein, m represents an integer of 1 to 5, J¹ represents a group XIVatom in the periodic table of the elements, R² represents a hydrogenatom, a halogen atom, an optionally substituted hydrocarbyl group having1 to 20 carbon atoms, an optionally substituted hydrocarbyloxy grouphaving 1 to 20 carbon atoms, a substituted silyl group having 1 to 20carbon atoms or a substituted amino group having 1 to 20 carbon atoms,and a plurality of R² may be mutually the same or different.)].

[wherein, M² represents a group IV transition metal atom in the periodictable of the elements, X², R³ and R⁴ represent each independently ahydrogen atom, a halogen atom, an optionally substituted hydrocarbylgroup having 1 to 20 carbon atoms, an optionally substitutedhydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silylgroup having 1 to 20 carbon atoms or a substituted amino group having 1to 20 carbon atoms, and a plurality of X² may be mutually the same ordifferent, a plurality of R³ may be mutually the same or different, aplurality of R⁴ may be mutually the same or different, and Q² representsa crosslinking group of the following general formula (4):

(wherein, n represents an integer of 1 to 5, J² represents a group XIVatom in the periodic table of the elements, R⁵ represents a hydrogenatom, a halogen atom, an optionally substituted hydrocarbyl group having1 to 20 carbon atoms, an optionally substituted hydrocarbyloxy grouphaving 1 to 20 carbon atoms, a substituted silyl group having 1 to 20carbon atoms or a substituted amino group having 1 to 20 carbon atoms,and a plurality of R⁵ may be mutually the same or different.)].

M¹ in the general formula (1) and M² in the general formula (3)represent a group IV transition metal atom in the periodic table of theelements, and examples thereof include a titanium atom, zirconium atom,hafnium atom and the like.

X¹, R¹ in the general formula (1) and X², R³, R⁴ in the general formula(3) represent each independently a hydrogen atom, a halogen atom, anoptionally substituted hydrocarbyl group having 1 to 20 carbon atoms, anoptionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms,a substituted silyl group having 1 to 20 carbon atoms or a substitutedamino group having 1 to 20 carbon atoms, and a plurality of X¹ may bemutually the same or different, a plurality of R¹ may be mutually thesame or different, a plurality of X² may be mutually the same ordifferent, a plurality of R³ may be mutually the same or different, anda plurality of R⁴ may be mutually the same or different.

The halogen atom represented by X¹, R¹, X², R³ and R⁴ includes afluorine atom, chlorine atom, bromine atom, iodine atom and the like.

The optionally substituted hydrocarbyl group having 1 to 20 carbon atomsrepresented by X¹, R¹, X², R³ and R⁴ includes an alkyl group having 1 to20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms,an aralkyl group having 7 to 20 carbon atoms, an aryl groups having 6 to20 carbon atoms, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms include a methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group,isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decylgroup, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group,n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecylgroup, n-heptadecyl group, n-octadecyl group, n-nonadecyl group,n-eicosyl group and the like.

Examples of the halogenated alkyl group having 1 to 20 carbon atomsinclude a fluoromethyl group, difluoromethyl group, trifluoromethylgroup, chloromethyl group, dichloromethyl group, trichloromethyl group,bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethylgroup, diiodomethyl group, triiodomethyl group, fluoroethyl group,difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group,pentafluoroethyl group, chloroethyl group, dichloroethyl group,trichloroethyl group, tetrachloroethyl group, pentachloroethyl group,bromoethyl group, dibromoethyl group, tribromoethyl group,tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,perfluorobutyl group, perfluoropentyl group, perfluorohexyl group,perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group,perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group,perchloropentyl group, perchlorohexyl group, perchlorooctyl group,perchlorododecyl group, perchloropentadecyl group, perchloroeicosylgroup, perbromopropyl group, perbromobutyl group, perbromopentyl group,perbromohexyl group, perbromooctyl group, perbromododecyl group,perbromopentadecyl group, perbromoeicosyl group and the like.

Examples of the aralkyl group having 7 to 20 carbon atoms include abenzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methylgroup, (4-methylphenyl)methyl group, (2,3-dimethylphenyl)methyl group,(2,4-dimethylphenyl)methyl group, (2,5-dimethylphenyl)methyl group,(2,6-dimethylphenyl)methyl group, (3,4-dimethylphenyl)methyl group,(4,6-dimethylphenyl)methyl group, (2,3,4-trimethylphenyl)methyl group,(2,3,5-trimethylphenyl)methyl group, (2,3,6-trimethylphenyl)methylgroup, (3,4,5-trimethylphenyl)methyl group,(2,4,6-trimethylphenyl)methyl group, (2,3,4,5-tetramethylphenyl)methylgroup, (2,3,4,6-tetramethylphenyl)methyl group,(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methylgroup, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,(sec-butylphenyl)methyl group, (tert-butylphenyl)methyl group,(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,(n-hexylphenyl)methyl group, (n-octylphenyl)methyl group,(n-decylphenyl)methyl group, (n-decylphenyl)methyl group,(n-tetradecylphenyl)methyl group, naphthylmethyl group,anthracenylmethyl group, phenylethyl group, phenylpropyl group,phenylbutyl group, diphenylmethyl group, diphenylethyl group,diphenylpropyl group, diphenylbutyl group and the like. Furthermentioned are halogenated aralkyl groups obtained by substitution onthese aralkyl groups with a halogen atom such as a fluorine atom,chlorine atom, bromine atom or iodine atom, and the like.

Examples of the aryl group having 6 to 20 carbon atoms include a phenylgroup, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group,2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group,3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenylgroup, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group,2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group,pentamethylphenyl group, ethylphenyl group, diethylphenyl group,triethylphenyl group, n-propylphenyl group, isopropylphenyl group,n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group,n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group,n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group,n-tetradecylphenyl group, naphthyl group, anthracenyl group and thelike. Further mentioned are halogenated aryl groups obtained bysubstitution on these aryl groups with a halogen atom such as a fluorineatom, chlorine atom, bromine atom or iodine atom, and the like.

The optionally substituted hydrocarbyl group having 1 to 20 carbon atomsincludes a hydrocarbyl group substituted with a substituted silyl group,a hydrocarbyl group substituted with a substituted amino group, ahydrocarbyl group substituted with a hydrocarbyloxy group, and the like.

The hydrocarbyl group substituted with a substituted silyl groupincludes a trimethylsilylmethyl group, trimethylsilylethyl group,trimethylsilylpropyl group, trimethylsilylbutyl group,trimethylsilylphenyl group, bis(trimethylsilyl)methyl group,bis(trimethylsilyl)ethyl group, bis(trimethylsilyl)propyl group,bis(trimethylsilyl)butyl group, bis(trimethylsilyl)phenyl group,triphenylsilylmethyl group and the like.

The hydrocarbyl group substituted with a substituted amino groupincludes a dimethylaminomethyl group, dimethylaminoethyl group,dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenylgroup, bis(dimethylamino)methyl group, bis(dimethylamino)ethyl group,bis(dimethylamino)propyl group, bis(dimethylamino)butyl group,bis(dimethylamino)phenyl group, phenylaminomethyl group,diphenylaminomethyl group, diphenylaminophenyl group and the like.

The hydrocarbyl group substituted with a hydrocarbyloxy group includes amethoxymethyl group, ethoxymethyl group, n-propoxymethyl group,isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group,tert-butoxymethyl group, phenoxymethyl group, methoxyethyl group,ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group,n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group,phenoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group,n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propylgroup, sec-butoxy-n-propyl group, tert-butoxy-n-propyl group,phenoxy-n-propyl group, methoxyisopropyl group, ethoxyisopropyl group,n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropylgroup, sec-butoxyisopropyl group, tert-butoxyisopropyl group,phenoxyisopropyl group, methoxyphenyl group, ethoxyphenyl group,n-propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group,sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group andthe like.

The optionally substituted hydrocarbyloxy group having 1 to 20 carbonatoms represented by X¹, R¹, X², R³ and R⁴ includes an alkoxy grouphaving 1 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbonatoms, aryloxy group having 6 to 20 carbon atoms, and the like.

Examples of the alkoxy group having 1 to 20 carbon atoms include amethoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxygroup, sec-butoxy group, tert-butoxy group, n-pentyloxy group,neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxygroup, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group,n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group,n-hexadecyloxy group, n-heptadecyloxy group, n-heptadecyloxy group,n-octadecyloxy group, n-nonadecyloxy group, n-eicosoxy group and thelike. Further mentioned are halogenated alkoxy groups obtained bysubstitution on these alkoxy groups with a halogen atom such as afluorine atom, chlorine atom, bromine atom or iodine atom, and the like.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include abenzyloxy group, (2-methylphenyl)methoxy group, (3-methylphenyl)methoxygroup, (4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group,(2,4-dimethylphenyl)methoxy group, (2,5-dimethylphenyl)methoxy group,(2,6-dimethylphenyl)methoxygroup, (3,4-dimethylphenyl)methoxy group,(3,5-dimethylphenyl)methoxy group, (2,3,4-trimethylphenyl)methoxy group,(2,3,5-trimethylphenyl)methoxy group, (2,3,6-trimethylphenyl)methoxygroup, (2,4,5-trimethylphenyl)methoxy group,(2,4,6-trimethylphenyl)methoxy group, (3,4,5-trimethylphenyl)methoxygroup, (2,3,4,5-tetramethylphenyl)methoxy group,(2,3,4,6-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, (ethylphenyl)methoxy group, (n-propylphenyl)methoxy group,(isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group,(sec-butylphenyl)methoxy group, (tert-butylphenyl)methoxy group,(n-hexylphenyl)methoxy group, (n-octylphenyl)methoxy group,(n-decylphenyl)methoxy group, (n-tetradecylphenyl)methoxy group,naphthylmethoxy group, anthracenylmethoxy group and the like. Furthermentioned are halogenated aralkyloxy groups obtained by substitution onthese aralkyloxy groups with a halogen atom such as a fluorine atom,chlorine atom, bromine atom or iodine atom, and the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include aphenoxy group, 2-methylphenoxy group, 3-methylphenoxy group,4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxygroup, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group,2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group,2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group,2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group,2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxygroup, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxygroup, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxygroup, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxygroup, naphthoxy group, anthracenoxy group and the like. Furthermentioned are halogenated aryloxy groups obtained by substitution onthese aryloxy groups with a halogen atom such as a fluorine atom,chlorine atom, bromine atom or iodine atom, and the like.

The substituted silyl group having 1 to 20 carbon atoms represented byX¹, R¹, X², R³ and R⁴ includes silyl groups substituted with ahydrocarbyl group such as an alkyl group, aryl group and the like.Specific examples thereof include mono-substituted silyl groups such asa methylsilyl group, ethylsilyl group, n-propylsilyl group,isopropylsilyl group, n-butylsilyl group, sec-butylsilyl group,tert-butylsilyl group, isobutylsilyl group, n-pentylsilyl group,n-hexylsilyl group, phenylsilyl group and the like; di-substituted silylgroups such as a dimethylsilyl group, diethylsilyl group,di-n-propylsilyl group, diisopropylsilyl group, di-n-butylsilyl group,di-sec-butylsilyl group, di-tert-butylsilyl group, diisobutylsilylgroup, diphenylsilyl group and the like; tri-substituted silyl groupssuch as a trimethylsilyl group, triethylsilyl group, tri-n-propylsilylgroup, triisopropylsilyl group, tri-n-butylsilyl group,tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilylgroup, tert-butyldimethylsilyl group, tri-n-pentylsilyl group,tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl groupand the like; etc.

Examples of the substituted amino group having 1 to 20 carbon atomsrepresented by X¹, R¹, X², R³ and R⁴ include amino groups substitutedwith two hydrocarbyl groups such as an alkyl group, aryl group and thelike. Specific examples thereof include a methylamino group, ethylaminogroup, n-propylamino group, isopropylamino group, n-butylamino group,sec-butylamino group, tert-butylamino group, isobutylamino group,n-hexylamino group, n-octylamino group, n-decylamino group, phenylaminogroup, benzylamino group, dimethylamino group, diethylamino group,di-n-propylamino group, diisopropylamino group, di-n-butylamino group,di-sec-butylamino group, di-tert-butylamino group, diisobutylaminogroup, tert-butylisopropylamino group, di-n-hexylamino group,di-n-octylamino group, di-n-decylamino group, diphenylamino group,dibenzylamino group, tert-butylisopropylamino group, phenylethylaminogroup, phenylpropylamino group, phenylbutylamino group, pyrrolyl group,pyrrolidiny group, piperidinyl group, carbazolyl group,dihydroisoindolyl group and the like.

X¹ represents preferably a chlorine atom, methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxygroup, n-propoxy group, isopropoxy group, n-butoxy group,trifluoromethoxy group, phenyl group, phenoxy group,2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group,pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxygroup or benzyl group.

R¹ represents preferably a hydrogen atom or alkyl group having 1 to 6carbon atoms, more preferably a hydrogen atom or alkyl group having 1 to4 carbon atoms, and further preferably a hydrogen atom.

X² represents preferably a chlorine atom, methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxygroup, n-propoxy group, isopropoxy group, n-butoxy group,trifluoromethoxy group, phenyl group, phenoxy group,2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group,pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxygroup or benzyl group.

R³ represents preferably a hydrogen atom or alkyl group having 1 to 6carbon atoms, more preferably a hydrogen atom or alkyl group having 1 to4 carbon atoms, and further preferably a hydrogen atom.

R⁴ represents preferably a hydrogen atom or alkyl group having 1 to 6carbon atoms, more preferably a hydrogen atom or alkyl group having 1 to4 carbon atoms, and further preferably a hydrogen atom.

Q¹ in the general formula (1) represents a crosslinking group of thegeneral formula (2), and Q² in the general formula (3) represents acrosslinking group of the general formula (4).

m in the general formula (2) and n in the general formula (4) representan integer of 1 to 5. m represents preferably 1 to 2, and n representspreferably 1 to 2.

J¹ in the general formula (2) and J² in the general formula (4)represent a group XIV transition metal atom in the periodic table of theelements, and include a carbon atom, silicon atom, germanium atom andthe like. Preferable is a carbon atom or silicon atom.

R² in the general formula (2) and R⁵ in the general formula (4)represent each independently a hydrogen atom, a halogen atom, anoptionally substituted hydrocarbyl group having 1 to 20 carbon atoms, anoptionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms,a substituted silyl group having 1 to 20 carbon atoms or a substitutedamino group having 1 to 20 carbon atoms, and a plurality of R² may bemutually the same or different and a plurality of R⁵ may be mutually thesame or different.

As the halogen atom, optionally substituted hydrocarbyl group having 1to 20 carbon atoms, optionally substituted hydrocarbyloxy group having 1to 20 carbon atoms, substituted silyl group having 1 to 20 carbon atomsand substituted amino group having 1 to 20 carbon atoms represented byR² and R⁵, there are mentioned those exemplified as the halogen atom,optionally substituted hydrocarbyl group having 1 to 20 carbon atoms,optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms,substituted silyl group having 1 to 20 carbon atoms and substitutedamino group having 1 to 20 carbon atoms represented by X¹, R¹, X², R³and R⁴.

Q¹ and Q² include a methylene group, ethylidene group, ethylene group,propylidene group, propylene group, butylidene group, butylene group,pentylidene group, pentylene group, hexylidene group, isopropylidenegroup, methylethylmethylene group, methylpropylmethylene group,methylbutylmethylene group, bis(cyclohexyl)methylene group,methylphenylmethylene group, diphenylmethylene group,phenyl(methylphenyl)methylene group, di(methylphenyl)methylene group,bis(dimethylphenyl)methylene group, bis(trimethylphenyl)methylene group,phenyl(ethylphenyl)methylene group, di(ethylphenyl)methylene group,bis(diethylphenyl)methylene group, phenyl(propylphenyl)methylene group,di(propylphenyl)methylene group, bis(dipropylphenyl)methylene group,phenyl(butylphenyl)methylene group, di(butylphenyl)methylene group,phenyl(naphthyl)methylene group, di(naphthyl)methylene group,phenyl(biphenyl)methylene group, di(biphenyl)methylene group,phenyl(trimethylsilylphenyl)methylene group,bis(trimethylsilylphenyl)methylene group,bis(pentafluorophenyl)methylene group, silanediyl group, disilanediylgroup, trisilanediyl group, tetrasilanediyl group, dimethylsilanediylgroup, bis(dimethylsilane)diyl group, diethylsilanediyl group,dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediylgroup, silacyclobutanediyl group, silacyclohexanediyl group,divinylsilanediyl group, diarylsilanediyl group,(methyl)(vinyl)silanediyl group, (aryl)(methyl)silanediyl group and thelike.

Q¹ represents preferably a methylene group, ethylene group,isopropylidene group, bis(cyclohexyl)methylene group, diphenylmethylenegroup, dimethylsilanediyl group or bis(dimethylsilane)diyl group, morepreferably an ethylene group or dimethylsilanediyl group. Q² representspreferably a methylene group, ethylene group, isopropylidene group,bis(cyclohexyl)methylene group, diphenylmethylene group,dimethylsilanediyl group or bis(dimethylsilane)diyl group, morepreferably a diphenylmethylene group.

As the transition metal compound (A1) of the general formula (1) inwhich M¹ represents a zirconium atom and X¹ represents a chlorine atom,exemplified are methylenebis(indenyl)zirconium dichloride,isopropylidenebis(indenyl)zirconium dichloride,(methyl)(phenyl)methylenebis(indenyl)zirconium dichloride,diphenylmethylenebis(indenyl)zirconium dichloride,ethylenebis(indenyl)zirconium dichloride,methylenebis(methylindenyl)zirconium dichloride,isopropylidenebis(methylindenyl)zirconium dichloride,(methyl)(phenyl)methylenebis(methylindenyl)zirconium dichloride,diphenylmethylenebis(methylindenyl)zirconium dichloride,ethylenebis(methylindenyl)zirconium dichloride,methylene(indenyl)(methylindenyl)zirconium dichloride,isopropylidene(indenyl)(methylindenyl)zirconium dichloride,(methyl)(phenyl)methylene(indenyl)(methylindenyl)zirconium dichloride,diphenylmethylene(indenyl)(methylindenyl)zirconium dichloride,ethylene(indenyl)(methylindenyl)zirconium dichloride,methylenebis(2,4-dimethylindenyl)zirconium dichloride,isopropylidenebis(2,4-dimethylindenyl)zirconium dichloride,(methyl)(phenyl)methylenebis(2,4-dimethylindenyl)zirconium dichloride,diphenylmethylenebis(2,4-dimethylindenyl)zirconium dichloride,ethylenebis(2,4-dimethylindenyl)zirconium dichloride,dimethylsilanediylbis(indenyl)zirconium dichloride,diethylsilanediylbis(indenyl)zirconium dichloride,di(n-propyl)silanediylbis(indenyl)zirconium dichloride,diisopropylsilanediylbis(indenyl)zirconium dichloride,dicyclohexylsilanediylbis(indenyl)zirconium dichloride,diphenylsilanediylbis(indenyl)zirconium dichloride,di(p-tolyl)silanediylbis(indenyl)zirconium dichloride,divinylsilanediylbis(indenyl)zirconium dichloride,diarylsilanediylbis(indenyl)zirconium dichloride,(methyl)(vinyl)silanediylbis(indenyl)zirconium dichloride,(aryl)(methyl)silanediylbis(indenyl)zirconium dichloride,(ethyl)(methyl)silanediylbis(indenyl)zirconium dichloride,(methyl)(n-propyl)silanediylbis(indenyl)zirconium dichloride,(methyl)(isopropyl)silanediylbis(indenyl)zirconium dichloride,(cyclohexyl)(methyl)bis(indenyl)zirconium dichloride,(methyl)(phenyl)silanediylbis(indenyl)zirconium dichloride,dimethylsilanediylbis(methylindenyl)zirconium dichloride,diethylsilanediylbis(methylindenyl)zirconium dichloride,di(n-propyl)silanediylbis(methylindenyl)zirconium dichloride,diisopropylsilanediylbis(methylindenyl)zirconium dichloride,dicyclohexylsilanediylbis(methylindenyl)zirconium dichloride,diphenylsilanediylbis(methylindenyl)zirconium dichloride,(ethyl)(methyl)silanediylbis(methylindenyl)zirconium dichloride,(methyl)(n-propyl)silanediylbis(methylindenyl)zirconium dichloride,(methyl)(isopropyl)silanediylbis(methylindenyl)zirconium dichloride,(cyclohexyl)(methyl)bis(methylindenyl)zirconium dichloride,(methyl)(phenyl)silanediylbis(methylindenyl)zirconium dichloride,dimethylsilanediyl(indenyl)(methylindenyl)zirconium dichloride,diethylsilanediyl(indenyl)(methylindenyl)zirconium dichloride,di(n-propyl)silanediyl(indenyl)(methylindenyl)zirconium dichloride,diisopropylsilanediyl(indenyl)(methylindenyl)zirconium dichloride,dicyclohexylsilanediyl(indenyl)(methylindenyl)zirconium dichloride,diphenylsilanediyl(indenyl)(methylindenyl)zirconium dichloride,(ethyl)(methyl)silanediyl(indenyl)(methylindenyl)zirconium dichloride,(methyl)(n-propyl)silanediyl(indenyl)(methylindenyl)zirconiumdichloride, (methyl)(isopropyl)silanediyl(indenyl)(methylindenyl)zirconium dichloride, (cyclohexyl)(methyl)(indenyl)(methylindenyl)zirconiumdichloride, (methyl)(phenyl)silanediyl(indenyl)(methylindenyl)zirconiumdichloride, dimethylsilanediylbis(2,4-dimethylindenyl)zirconiumdichloride, diethylsilanediylbis(2,4-dimethylindenyl)zirconiumdichloride, di(n-propyl)silanediylbis(2,4-dimethylindenyl)zirconiumdichloride, diisopropylsilanediylbis(2,4-dimethylindenyl)zirconiumdichloride, dicyclohexylsilanediylbis(2,4-dimethylindenyl)zirconiumdichloride, diphenylsilanediylbis(2,4-dimethylindenyl)zirconiumdichloride, (ethyl)(methyl)silanediylbis(2,4-dimethylindenyl)zirconiumdichloride,(methyl)(n-propyl)silanediylbis(2,4-dimethylindenyl)zirconiumdichloride,(methyl)(isopropyl)silanediylbis(2,4-dimethylindenyl)zirconiumdichloride, (cyclohexyl)(methyl)bis(2,4-dimethylindenyl)zirconiumdichloride, (methyl)(phenyl)silanediylbis(2,4-dimethylindenyl)zirconiumdichloride, and the like.

The substituted moieties of a η⁵-indenyl group in the above-describedexemplification include substituted moieties at 2-position, 3-position,4-position, 5-position, 6-position and 7-position in the case ofmono-substituted moieties when a crosslinking group is situated at1-position, and even if a crosslinking group is situated at positionsother than 1-position, likewise include all combinations. In the case ofdi- or more-substituted moieties, all combinations of substituents andcrosslink positions are included likewise. Further exemplified arecompounds obtained by changing dichloride X¹ in the above-describedtransition metal compounds into difluoride, dibromide, diiodide,dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide,dibutoxide, bis(trifluoromethoxide), diphenyl, diphenoxide,bis(2,6-di-tert-butylphenoxide), bis(3,4,5-trifluorophenoxide),bis(pentafluorophenoxide),bis(2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), dibenzyl and thelike. Moreover, compounds obtained by changing zirconium M¹ in theabove-described transition metal compounds into titanium or hafnium areexemplified.

As the transition metal compound (A1) of the general formula (1),preferable are ethylenebis(indenyl)zirconium diphenoxide,ethylenebis(indenyl)zirconium dichloride anddimethylsilylenebis(indenyl)zirconium dichloride.

As the transition metal compound (A2) of the general formula (3) inwhich M² represents a zirconium atom, X² represents a chlorine atom andthe crosslinking group Q² is diphenylmethylene group, exemplified arediphenylmethylene(1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride,diphenylmethylene(2-methyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-methyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-dimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-dimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride, diphenylmethylene(3,4-dimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride,diphenylmethylene(2,3,4-trimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-trimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-trimethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride,diphenylmethylene(2-ethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-ethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraethyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-di-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-di-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-di-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tri-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tri-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tri-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetra-n-propyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-isopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-isopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraisopropyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-phenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraphenyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-trimethylsilyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-bis(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-bis(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-bis(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tris(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tris(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tris(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetrakis(trimethylsilyl)-1-cyclopentadienyl)(9-fluorenyl)zirconiumdichloride,diphenylmethylene(1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-methyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-methyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-dimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-dimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-dimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-trimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-trimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-trimethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetramethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-ethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-ethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraethyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-di-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-di-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-di-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tri-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tri-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tri-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetra-n-propyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-isopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-isopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraisopropyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-phenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraphenyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-trimethylsilyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetrakis(trimethylsilyl)-1-cyclopentadienyl)(2,7-dimethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-methyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-methyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-dimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-dimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-dimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-trimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-trimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-trimethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetramethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-ethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-ethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraethyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-di-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-di-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-di-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tri-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tri-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tri-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetra-n-propyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-isopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-isopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraisopropyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-phenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraphenyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-trimethylsilyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetrakis(trimethylsilyl)-1-cyclopentadienyl)(2,7-diethyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-dimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-dimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-dimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-trimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-trimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-trimethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetramethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-ethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-ethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraethyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-di-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-di-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-di-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tri-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tri-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tri-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetra-n-propyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-isopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-isopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraisopropyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-phenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-diphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-diphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-diphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-triphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-triphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-triphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetraphenyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2-trimethylsilyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,5-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4-bis(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(3,4,5-tris(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride,diphenylmethylene(2,3,4,5-tetrakis(trimethylsilyl)-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconiumdichloride, and the like.

Compounds obtained by changing dichloride X²in the above-describedtransition metal compound into difluoride, dibromide, diiodide,dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide,dibutoxide, bis(trifluoromethoxide), diphenyl, diphenoxide,bis(2,6-di-tert-butylphenoxide), bis(3,4,5-trifluorophenoxide),bis(pentafluorophenoxide),bis(2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), dibenzyl and thelike are exemplified. Further, compounds obtained by changing thediphenylmethylene group Q² in the above-described transition metalcompound into a methylene group, ethylene group, isopropylidene group,methylphenylmethylene group, dimethylsilanediyl group,diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediylgroup and the like are exemplified. Moreover, compounds obtained bychanging zirconium M² in the above-described transition metal compoundinto titanium or hafnium are also exemplified.

As the transition metal compound (A2) of the general formula (3),preferable isdiphenylmethylene(1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride.

As the cocatalyst component (B) to be used for preparation of apolymerization catalyst used in production of the ethylene-α-olefincopolymer of the present invention, solid catalyst components formed bybringing the following component (b1), the following component (b2), thefollowing component (b3) and the following component (b4) into contactare mentioned.

(b1): a compound of the following general formula (5):

M³L_(x)   (5)

[wherein, M³ represents a lithium atom, sodium atom, potassium atom,rubidium atom, cesium atom, beryllium atom, magnesium atom, calciumatom, strontium atom, barium atom, zinc atom, germanium atom, tin atom,lead atom, antimony atom or bismuth atom, and x represents a numbercorresponding to the atomic valence of M³. L represents a hydrogen atom,halogen atom or optionally substituted hydrocarbyl group, and when thereexist a plurality of L, these may be mutually the same or different.]

(b2): a compound of the following general formula (6):

R⁶ _(t-1)T¹H   (6)

[wherein, T¹ represents an oxygen atom, sulfur atom, nitrogen atom orphosphorus atom, t represents a number corresponding to the atomicvalence of T¹. R⁶ represents a halogen atom, electron attractive group,halogen atom-containing group or electron attractive group-containinggroup, and when there exist a plurality of R⁶, these may be mutually thesame or different.]

(b3): a compound of the following general formula (7):

R⁷ _(s-2)T²H₂   (7)

[wherein, T² represents an oxygen atom, sulfur atom, nitrogen atom orphosphorus atom, and s represents a number corresponding to the atomicvalence of T². R⁷ represents a halogen atom, hydrocarbyl group orhalogenated hydrocarbyl group.]

(b4): a particulate carrier

M³ in the general formula (5) represents a lithium atom, sodium atom,potassium atom, rubidium atom, cesium atom, beryllium atom, magnesiumatom, calcium atom, strontium atom, barium atom, zinc atom, germaniumatom, tin atom, lead atom, antimony atom or bismuth atom. M³ representspreferably a magnesium atom, calcium atom, strontium atom, barium atom,zinc atom, germanium atom, tin atom or bismuth atom, more preferably amagnesium atom, zinc atom, tin atom or bismuth atom, and furtherpreferably a zinc atom.

x in the general formula (5) represents a number corresponding to theatomic valence of M³. For example, when M³ represents a zinc atom, xrepresents 2.

L in the general formula (5) represents a hydrogen atom, halogen atom oroptionally substituted hydrocarbyl group, and when there exist aplurality of L, these may be mutually the same or different.

The halogen atom represented by L includes a fluorine atom, chlorineatom, bromine atom, iodine atom and the like.

The optionally substituted hydrocarbyl group represented by L includesan alkyl group, aralkyl group, aryl group, halogenated alkyl group andthe like.

The alkyl group represented by L is preferably an alkyl group having 1to 20 carbon atoms, and examples thereof include a methyl group, ethylgroup, n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group,isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decylgroup, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group,n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecylgroup, n-heptadecyl group, n-octadecyl group, n-nonadecyl group,n-eicosyl group and the like. Preferably, it is a methyl group, ethylgroup, isopropyl group, tert-butyl group or isobutyl group.

The halogenated alkyl group represented by L is preferably a halogenatedalkyl group having 1 to 20 carbon atoms, and examples thereof include afluoromethyl group, difluoromethyl group, trifluoromethyl group,chloromethyl group, dichloromethyl group, trichloromethyl group,bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethylgroup, diiodomethyl group, triiodomethyl group, fluoroethyl group,difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group,pentafluoroethyl group, chloroethyl group, dichloroethyl group,trichloroethyl group, tetrachloroethyl group, pentachloroethyl group,bromoethyl group, dibromoethyl group, tribromoethyl group,tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,perfluorobutyl group, perfluoropentyl group, perfluorohexyl group,perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group,perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group,perchloropentyl group, perchlorohexyl group, perchlorooctyl group,perchlorododecyl group, perchloropentadecyl group, perchloroeicosylgroup, perbromopropyl group, perbromobutyl group, perbromopentyl group,perbromohexyl group, perbromooctyl group, perbromododecyl group,perbromopentadecyl group, perbromoeicosyl group and the like.

The aralkyl group represented by L is preferably an aralkyl group having7 to 20 carbon atoms, and examples thereof include a benzyl group,(2-methylphenyl)methyl group, (3-methylphenyl)methyl group,(4-methylphenyl)methyl group, (2,3-dimethylphenyl)methyl group,(2,4-dimethylphenyl)methyl group, (2,5-dimethylphenyl)methyl group,(2,6-dimethylphenyl)methyl group, (3,4-dimethylphenyl)methyl group,(4,6-dimethylphenyl)methyl group, (2,3,4-trimethylphenyl)methyl group,(2,3,5-trimethylphenyl)methyl group, (2,3,6-trimethylphenyl)methylgroup, (3,4,5-trimethylphenyl)methyl group,(2,4,6-trimethylphenyl)methyl group, (2,3,4,5-tetramethylphenyl)methylgroup, (2,3,4,6-tetramethylphenyl)methyl group,(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methylgroup, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,(sec-butylphenyl)methyl group, (tert-butylphenyl) methyl group,(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,(n-hexylphenyl)methyl group, (n-octylphenyl)methyl group,(n-decylphenyl)methyl group, (n-decylphenyl)methyl group,(n-tetradecylphenyl)methyl group, naphthylmethyl group,anthracenylmethyl group, phenylethyl group, phenylpropyl group,phenylbutyl group, diphenylmethyl group, diphenylethyl group,diphenylpropyl group, diphenylbutyl group and the like. Preferable is abenzyl group. Further mentioned are halogenated aralkyl groups having 7to 20 carbon atoms obtained by substitution on these aralkyl groups witha halogen atom such as a fluorine atom, chlorine atom, bromine atom oriodine atom, and the like.

The aryl group represented by L is preferably an aryl group having 6 to20 carbon atoms, and examples thereof include a phenyl group, 2-tolylgroup, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group,2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group,2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group,2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group,2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group,pentamethylphenyl group, ethylphenyl group, diethylphenyl group,triethylphenyl group, n-propylphenyl group, isopropylphenyl group,n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group,n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group,n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group,n-tetradecylphenyl group, naphthyl group, anthracenyl group and thelike. Preferable is a phenyl group. Further mentioned are halogenatedaryl groups having 6 to 20 carbon atoms obtained by substitution onthese aryl groups with a halogen atom such as a fluorine atom, chlorineatom, bromine atom or iodine atom, and the like.

L represents preferably a hydrogen atom, alkyl group or aryl group, morepreferably a hydrogen atom or alkyl group, and further preferably analkyl group.

T¹ in the general formula (6) represents an oxygen atom, sulfur atom,nitrogen atom or phosphorus atom, preferably a nitrogen atom or oxygenatom, more preferably an oxygen atom.

t in the general formula (6) represents the atomic valence of T¹, andwhen T¹ represents an oxygen atom or sulfur atom, t is 2 and when T¹represents a nitrogen atom or phosphorus atom, t is 3.

R⁶ in the general formula (6) represents a halogen atom, electronattractive group, halogen atom-containing group, electron attractivegroup-containing group or electron attractive group, and when thereexist a plurality of R⁶, these may be mutually the same or different. Asan index of electron attractivity, the Hammett's rule substituentconstant σ is known, and functional groups having positive Hammett'srule substituent constant σ are mentioned as the electron attractivegroup.

The halogen atom represented by R⁶ includes a fluorine atom, chlorineatom, bromine atom, iodine atom and the like.

The electron attractive group represented by R⁶ includes a cyano group,nitro group, carbonyl group, hydrocarbyloxycarbonyl group, sulfonegroup, phenyl group and the like.

The halogen atom-containing group represented by R⁶ includes halogenatedhydrocarbyl groups such as a halogenated alkyl group, halogenatedaralkyl group, halogenated aryl group, (halogenated alkyl)aryl group andthe like; halogenated hydrocarbyloxy groups; halogenatedhydrocarbyloxycarbonyl groups and the like. The electron attractivegroup-containing group represented by R⁶ includes cyanated hydrocarbylgroups such as a cyanated aryl group and the like, nitrated hydrocarbylgroups such as a nitrated aryl group and the like, etc.

The halogenated alkyl group represented by R⁶ includes a fluoromethylgroup, chloromethyl group, bromomethyl group, iodomethyl group,difluoromethyl group, dichloromethyl group, dibromomethyl group,diiodomethyl group, trifluoromethyl group, trichloromethyl group,tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group,2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group,2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group,2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group,2,2,3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethylgroup, 2,2,2-trichloro-1-trichloromethylethyl group,2,2,2-tribromo-1-tribromomethylethyl group,2,2,2-triiodo-1-triiodomethylethyl group,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group,1,1-bis(trichloromethyl)-2,2,2-trichloroethyl group,1,1-bis(tribromomethyl)-2,2,2-tribromoethyl group,1,1-bis(triiodomethyl)-2,2,2-triiodoethyl group and the like.

The halogenated aryl group represented by R⁶ includes a 2-fluorophenylgroup, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenylgroup, 2,6-difluorophenyl group, 3,4-difluorophenyl group,3,5-difluorophenyl group, 2,4,6-trifluorophenyl group,3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group,pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenylgroup, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group,perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, 2-chlorophenylgroup, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenylgroup, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group,3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group,3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group,pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenylgroup, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group,perchloro-1-naphthyl group, perchloro-2-naphthyl group, 2-bromophenylgroup, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenylgroup, 2,6-dibromophenyl group, 3,4-dibromophenyl group,3,5-dibromophenyl group, 2,4,6-tribromophenyl group,3,4,5-tribromophenyl group, 2,3,5,6-tetrabromophenyl group,pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group,2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthylgroup, perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenylgroup, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenylgroup, 3,4-diiodophenyl group, 3,5-diiodophenyl group,2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group,2,3,5,6-tetraiodophenyl group, pentaiodophenyl group,2,3,5,6-tetraiodo-4-triiodomethylphenyl group,2,3,5,6-tetraiodo-4-pentaiodophenyl group, periodo-1-naphthyl group,periodo-2-naphthyl group and the like.

The (halogenated alkyl)aryl group represented by R⁶ includes a2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group,4-(trifluoromethyl)phenyl group, 2,6-bis(trifluoromethyl)phenyl group,3,5-bis(trifluoromethyl)phenyl group, 2,4,6-tris(trifluoromethyl)phenylgroup, 3,4,5-tris(trifluoromethyl)phenyl group and the like.

The cyanated aryl group represented by R⁶ includes a 2-cyanophenylgroup, 3-cyanophenyl group, 4-cyanophenyl group and the like.

The nitrated aryl group represented by R⁶ includes a 2-nitrophenylgroup, 3-nitrophenyl group, 4-nitrophenyl group and the like.

The hydrocarbyloxycarbonyl group represented by R⁶ includes analkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl groupand the like, more specifically a methoxycarbonyl group, ethoxycarbonylgroup, n-propoxycarbonyl group, isopropoxycarbonyl group,phenoxycarbonyl group and the like.

The halogenated hydrocarbyloxycarbonyl group represented by R⁶ includesa halogenated alkoxycarbonyl group, halogenated aralkyloxycarbonylgroup, halogenated aryloxycarbonyl group and the like, more specificallya trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group andthe like.

R⁶ represents preferably a halogenated hydrocarbyl group, morepreferably a halogenated alkyl group or halogenated aryl group, furtherpreferably a fluorinated alkyl group, fluorinated aryl group,chlorinated alkyl group or chlorinated aryl group, and particularlypreferably a fluorinated alkyl group or fluorinated aryl group. Thefluorinated alkyl group is preferably a fluoromethyl group,difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group,2,2,3,3,3-pentafluoropropyl group,2,2,2-trifluoro-1-trifluoromethylethyl group or1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, more preferably atrifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group or1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl group. The fluorinatedaryl group is preferably a 2-fluorophenyl group, 3-fluorophenyl group,4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenylgroup, 3,4-difluorophenyl group, 3,5-difluorophenyl group,2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group,2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group,2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group,2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group,perfluoro-1-naphthyl group or perfluoro-2-naphthyl group, morepreferably a 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group orpentafluorophenyl group. The chlorinated alkyl group is preferably achloromethyl group, dichloromethyl group, trichloromethyl group,2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group,2,2,2-trichloro-1-trichloromethylethyl group or1,1-bis(trichloromethyl)-2,2,2-trichloroethyl group. The chlorinatedaryl group is preferably a 4-chlorophenyl group, 2,6-dichlorophenylgroup, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group,3,4,5-trichlorophenyl group or pentachlorophenyl group.

T² in the general formula (7) represents an oxygen atom, sulfur atom,nitrogen atom or phosphorus atom, preferably a nitrogen atom or oxygenatom, more preferably an oxygen atom.

s in the general formula (7) represents the atomic valence of T², andwhen T² represents an oxygen atom or sulfur atom, s is 2 and when T²represents a nitrogen atom or phosphorus atom, s is 3.

R⁷ in the general formula (7) represents a hydrocarbyl group orhalogenated hydrocarbyl group. The hydrocarbyl group represented by R⁷includes an alkyl group, aralkyl group, aryl group and the like, andexemplified are those exemplified as the alkyl group, aralkyl group andaryl group represented by L. The halogenated hydrocarbyl grouprepresented by R⁷ includes halogenated hydrocarbyl groups such as ahalogenated alkyl group, halogenated aralkyl group, halogenated arylgroup, (halogenated alkyl)aryl group and the like, and exemplified arethose exemplified as the halogenated alkyl group, halogenated aryl groupand (halogenated alkyl)aryl group represented by R⁶.

R⁷ represents preferably a halogenated hydrocarbyl group, morepreferably a fluorinated hydrocarbyl group.

The compound of the general formula (5) in which M³ represents a zincatom as the component (b1) includes dialkylzincs such as dimethylzinc,diethylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc,diisobutylzinc, di-n-hexylzinc and the like; diarylzincs such asdiphenylzinc, dinaphthylzinc, bis(pentafluorophenyl)zinc and the like;dialkenylzincs such as diarylzinc and the like;bis(cyclopentadienyl)zinc; halogenated alkylzincs such as methylzincchloride, ethylzinc chloride, n-propylzinc chloride, isopropylzincchloride, n-butylzinc chloride, isobutylzinc chloride, n-hexylzincchloride, methylzinc bromide, ethylzinc bromide, n-propylzinc bromide,isopropylzinc bromide, n-butylzinc bromide, isobutylzinc bromide,n-hexylzinc bromide, methylzinc iodide, ethylzinc iodide, n-propylzinciodide, isopropylzinc iodide, n-butylzinc iodide, isobutylzinc iodide,n-hexylzinc iodide and the like; halogenated zincs such as zincfluoride, zinc chloride, zinc bromide, zinc iodide and the like, etc.

The compound of the general formula (5) as the component (b1) ispreferably dialkylzinc, further preferably dimethylzinc, diethylzinc,di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc ordi-n-hexylzinc, and particularly preferably dimethylzinc or diethylzinc.

The compound of the general formula (6) as the component (b2) includesan amine, phosphine, alcohol, thiol, phenol, thiophenol, naphthol,naphthylthiol, carboxylic acid compound and the like.

The amine includes di(fluoromethyl)amine, bis(difluoromethyl)amine,bis(trifluoromethyl)amine, bis(2,2,2-trifluoroethyl)amine,bis(2,2,3,3,3-pentafluoropropyl)amine,bis(2,2,2-trifluoro-1-trifluoromethylethyl)amine,bis(1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine,bis(2-fluorophenyl)amine, bis(3-fluorophenyl)amine,bis(4-fluorophenyl)amine, bis(2,6-difluorophenyl)amine,bis(3,5-difluorophenyl)amine, bis(2,4,6-trifluorophenyl)amine,bis(3,4,5-trifluorophenyl)amine, bis(pentafluorophenyl)amine,bis(2-(trifluoromethyl)phenyl)amine, bis(3-(trifluoromethyl)phenyl)amine, bis (4-(trifluoromethyl)phenyl)aminebis(2,6-di(trifluoromethyl)phenyl)amine,bis(3,5-di(trifluoromethyl)phenyl)amine,bis(2,4,6-tri(trifluoromethyl)phenyl)amine, bis(2-cyanophenyl)amine,(3-cyanophenyl)amine, bis(4-cyanophenyl)amine, bis(2-nitrophenyl)amine,bis(3-nitrophenyl)amine, bis(4-nitrophenyl)amine,bis(1H,1H-perfluorobutyl)amine, bis(1H,1H-perfluoropentyl)amine,bis(1H,1H-perfluorohexyl)amine, bis(1H,1H-perfluorooctyl)amine,bis(1H,1H-perfluorododecyl)amine, bis(1H,1H-perfluoropentadecyl)amine,bis(1H,1H-perfluoroeicosyl)amine and the like. Further mentioned areamines obtained by changing fluoro in these amines into chloro, bromo oriodo.

As the phosphine, compounds obtained by changing a nitrogen atom in theabove-described amines into a phosphorus atom are mentioned. Thesephosphines are compounds obtained by substituting amine in theabove-described amines by phosphine.

The alcohol includes fluoromethanol, difluoromethanol,trifluoromethanol, 2,2,2-trifluoroethanol,2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol, 1H,1H-perfluorobutanol,1H,1H-perfluoropentanol, 1H,1H-perfluorohexanol, 1H,1H-perfluorooctanol,1H,1H-perfluorododecanol, 1H,1H-perfluoropentadecanol,1H,1H-perfluoroeicosanol and the like. Further mentioned are alcoholsobtained by changing fluoro in these alcohols into chloro, bromo oriodo.

As the thiol, compounds obtained by changing an oxygen atom in theabove-described alcohols into a sulfur atom are mentioned. These thiolsare compounds obtained by substituting nol in the above-describedalcohols by nethiol.

The phenol includes 2-fluorophenol, 3-fluorophenol, 4-fluorophenol,2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol,3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol,2,3,5,6-tetrafluorophenol, pentafluorophenol,2,3,5,6-tetrafluoro-4-trifluoromethylphenol,2,3,5,6-tetrafluoro-4-pentafluorophenylphenol and the like. Furthermentioned are phenols obtained by changing fluoro in these phenols intochloro, bromo or iodo.

As the thiophenol, compounds obtained by changing an oxygen atom in theabove-described phenols into a sulfur atom are mentioned. Thesethiophenols are compounds obtained by substituting phenol in theabove-described phenols by thiophenol.

The naphthol includes perfluoro-1-naphthol, perfluoro-2-naphthol,4,5,6,7,8-pentafluoro-2-naphthol, 2-(trifluoromethyl)phenol,3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol,2,6-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol,2,4,6-tris(trifluoromethyl)phenol, 2-cyanophenol, 3-cyanophenol,4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like.Further mentioned are naphthols obtained by changing fluoro in thesenaphthols into chloro, bromo or iodo.

As the naphthylthiol, compounds obtained by changing an oxygen atom inthe above-described naphthols into a sulfur atom are mentioned. Thesenaphthylthiols are compounds obtained by substituting naphthol in theabove-described naphthols by naphthylthiol.

Examples of the carboxylic acid compound include pentafluorobenzoicacid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoicacid, perfluoropentanoic acid, perfluorohexanoic acid,perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid,perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoicacid and the like.

The compound of the general formula (6) as the component (b2) ispreferably an amine, alcohol or phenol compound, and the amine ispreferably bis(trifluoromethyl)amine, bis(2,2,2-trifluoroethyl)amine,bis(2,2,3,3,3-pentafluoropropyl)amine,bis(2,2,2-trifluoro-1-trifluoromethylethyl)amine,bis(1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine orbis(pentafluorophenyl)amine, the alcohol is preferablytrifluoromethanol, 2,2,2-trifluoroethanol,2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanolor 1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol, and the phenol ispreferably 2-fluorophenol, 3-fluorophenol, 4-fluorophenol,2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol,3,4,5-trifluorophenol, pentafluorophenol, 2-(trifluoromethyl)phenol,3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol,2,6-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol,2,4,6-tris(trifluoromethyl)phenol or 3,4,5-tris(trifluoromethyl)phenol.

The compound of the general formula (6) as the component (b2) is morepreferably bis(trifluoromethyl)amine, bis(pentafluorophenyl)amine,trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol, 2-fluorophenol,3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol,2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol,4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol or2,4,6-tris(trifluoromethyl)phenol, further preferably3,5-difluorophenol, 3,4,5-trifluorophenol, pentafluorophenol or1,1-bis(trifluoromethyl)-2,2,2-trifluoroethanol.

The compound of the general formula (7) as the component (b3) includeswater, hydrogen sulfide, amine, aniline compound and the like.

The amine includes alkylamines such as methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, sec-butylamine,tert-butylamine, isobutylamine, n-pentylamine, neopentylamine,isopentylamine, n-hexylamine, n-octylamine, n-decylamine,n-dodecylamine, n-pentadecylamine, n-eicosylamine and the like;aralkylamines such as benzylamine, (2-methylphenyl)methylamine,(3-methylphenyl)methylamine, (4-methylphenyl)methylamine,(2,3-dimethylphenyl)methylamine, (2,4-dimethylphenyl)methylamine,(2,5-dimethylphenyl)methylamine, (2,6-dimethylphenyl)methylamine,(3,4-dimethylphenyl)methylamine, (3,5-dimethylphenyl)methylamine,(2,3,4-trimethylphenyl)methylamine, (2,3,5-trimethylphenyl)methylamine,(2,3,6-trimethylphenyl)methylamine, (3,4,5-trimethylphenyl)methylamine,(2,4,6-trimethylphenyl)methylamine,(2,3,4,5-tetramethylphenyl)methylamine,(2,3,4,6-tetramethylphenyl)methylamine,(2,3,5,6-tetramethylphenyl)methylamine, (pentamethylphenyl)methylamine,(ethylphenyl)methylamine, (n-propylphenyl)methylamine,(isopropylphenyl)methylamine, (n-butylphenyl)methylamine,(sec-butylphenyl)methylamine, (tert-butylphenyl)methylamine,(n-pentylphenyl)methylamine, (neopentylphenyl)methylamine,(n-hexylphenyl)methylamine, (n-octylphenyl)methylamine,(n-decylphenyl)methylamine, (n-tetradecylphenyl)methylamine,naphthylmethylamine, anthracenylmethylamine and the like; arylamines;cyclopentadienylamines; and the like.

Further, the amine includes halogenated alkylamines such asfluoromethylamine, difluoromethylamine, trifluoromethylamine,2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine,2,2,2-trifluoro-1-trifluoromethylethylamine,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethylamine,perfluoropropylamine, perfluorobutylamine, perfluoropentylamine,perfluorohexylamine, perfluorooctylamine, perfluorododecylamine,perfluoropentadecylamine, perfluoroeicosylamine and the like. Furthermentioned are amines obtained by changing fluoro in these amines intochloro, bromo or iodo.

The aniline compound includes aniline, naphthylamine, anthracenylamine,2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline,2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline,3,4-dimethylaniline, 3,5-dimethylaniline, 2,3,4-trimethylaniline,2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline,3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline,2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline,pentamethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline,2,3-diethylaniline, 2,4-diethylaniline, 2,5-diethylaniline,2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline,2,3,4-triethylaniline, 2,3,5-triethylaniline, 2,3,6-triethylaniline,2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline,2,3,4,6-tetraethylaniline, 2,3,5,6-tetraethylaniline, pentaethylanilineand the like. Further mentioned are aniline compounds obtained bychanging ethyl in these aniline compounds into n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl,n-decyl, n-dodecyl, n-tetradecyl and the like.

The aniline compound includes 2-fluoroaniline, 3-fluoroaniline,4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline,2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline,2-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline,4-(trifluoromethyl)aniline, 2,6-di(trifluoromethyl)aniline,3,5-di(trifluoromethyl)aniline, 2,4,6-tri(trifluoromethyl)aniline,3,4,5-tri(trifluoromethyl)aniline and the like. Further mentioned areaniline compounds obtained by changing fluoro in these aniline compoundsinto chloro, bromo, iodo and the like.

The compound of the general formula (7) as the component (b3) ispreferably water, hydrogen sulfide, methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, sec-butylamine,tert-butylamine, isobutylamine, n-octylamine, aniline,2,6-dimethylaniline, 2,4,6-trimethylaniline, naphthylamine,anthracenylamine, benzylamine, trifluoromethylamine,pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine,perfluoropentylamine, perfluorohexylamine, perfluorooctylamine,perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine,2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline,3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline,pentafluoroaniline, 2-(trifluoromethyl)aniline,3-(trifluoromethyl)aniline, 4-(trifluoromethyl)aniline,2,6-bis(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline,2,4,6-tris(trifluoromethyl)aniline or3,4,5-tris(trifluoromethyl)aniline, particularly preferably water,trifluoromethylamine, perfluorobutylamine, perfluorooctylamine,perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline,4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline,2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline,2-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline,4-(trifluoromethyl)aniline, 2,6-bis(trifluoromethyl)aniline,3,5-bis(trifluoromethyl)aniline, 2,4,6-tris(trifluoromethyl)aniline or3,4,5-tris(trifluoromethyl)aniline, and most preferably water orpentafluoroaniline.

As the particulate carrier as the component (b4), solvents forpreparation of polymerization catalysts or solid substances insoluble ina polymerization solvent are suitably used, porous substances are moresuitably used, inorganic substances or organic polymers are furthersuitably used, and inorganic substances are particularly suitably used.

The particulate carrier as the component (b4) is preferably a carrierhaving uniform particle size, and the volume-based geometric standarddeviation of the particle size of the particulate carrier as thecomponent (b4) is preferably 2.5 or less, more preferably 2.0 or less,and further preferably 1.7 or less.

As the inorganic substance as the particulate carrier as the component(b4), inorganic oxides, clays, clay minerals and the like are mentioned.Some of them may also be used in admixture.

The inorganic oxide includes SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO,ZnO, BaO, ThO₂, SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃,SiO₂—TiO₂—MgO, and mixtures composed of two or more of them. Of theseinorganic oxides, SiO₂ and/or Al₂O₃ is preferable, and particularly,SiO₂ (silica) is preferable. The above-described inorganic oxides maycontain a small amount of carbonate, sulfate, nitrate or oxidecomponents such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃,BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O, Li₂O and the like.

Though a hydroxyl group is usually generated and present on the surfaceof the inorganic oxide, modified inorganic oxides obtained bysubstituting active hydrogen of the surface hydroxyl group by varioussubstituents may also be used as the inorganic oxide. Examples of themodified inorganic oxide include inorganic oxides brought into contactwith a trialkylchlorosilane such as trimethylchlorosilane,tert-butyldimethylchlorosilane and the like; a triarylchlorosilane suchas triphenylchlorosilane and the like; a dialkyldichlorosilane such asdimethyldichlorosilane and the like; a diaryldichlorosilane such asdiphenyldichlorosilane and the like; an alkyltrichlorosilane such asmethyltrichlorosilane and the like; an aryltrichlorosilane such asphenyltrichlorosilane and the like; a trialkylalkoxysilane such astrimethylmethoxysilane and the like; a triarylalkoxysilane such astriphenylmethoxysilane and the like; a dialkyldialkoxysilane such asdimethyldimethoxysilane and the like; a diaryldialkoxysilane such asdiphenyldimethoxysilane and the like; an alkyltrialkoxysilane such asmethyltrimethoxysilane and the like; an aryltrialkoxysilane such asphenyltrimethoxysilane and the like; a tetraalkoxysilane such astetramethoxysilane and the like; an alkyldisilazane such as1,1,1,3,3,3-hexamethyldisilazane and the like; tetrachlorosilane; analcohol such as methanol, ethanol and the like; phenol; adialkylmagnesium such as dibutylmagnesium, butylethylmagnesium,butyloctylmagnesium and the like; an alkyllithium such as butyllithiumand the like, etc.

Further exemplified are inorganic oxides obtained by contacting with adialkylamine such as diethylamine, diphenylamine and the like, analcohol such as methanol, ethanol and the like, or phenol, aftercontacting with a trialkylaluminum.

In some cases, hydroxyl groups in an inorganic oxide are mutuallyhydrogen-bonded to enhance the strength of the inorganic oxide itself.In this case, if all active hydrogens of surface hydroxyl groups aresubstituted by various substituents, lowering of the particle strengthand the like occur in some cases. Therefore, it is not necessarilyrequired to substitute all active hydrogens of surface hydroxyl groupson an inorganic oxide, and the substitution ratio of surface hydroxylgroups may be appropriately determined. The method of changing thesubstitution ratio of surface hydroxyl groups is not particularlyrestricted. As this method, for example, a method of varying the useamount of a compound to be used for contacting is exemplified.

The clay or clay mineral includes kaolin, bentonite, kibushi-clay,gairome clay, allophane, hisingerite, bairofiraito, talc, micas,smectite, montmorillonites, hectorite, laponite, vermiculite, chlorites,palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Ofthem, preferable are smectite, montmorillonite, hectorite, laponite andsaponite, further preferable are montmorillonite and hectorite.

As the inorganic substance, inorganic oxides are suitably used. It ispreferable that the inorganic substance is dried to substantially removewater, and those dried by a heating treatment are preferable. Theheating treatment is carried out at a temperature of 100 to 1500° C.,preferably 100 to 1000° C., further preferably 200 to 800° C., usually,for an inorganic substance of which water content cannot be visuallyconfirmed. The heating time is preferably 10 minutes to 50 hours, morepreferably 1 hour to 30 hours. The heat dry method includes a method inwhich a dried inert gas (for example, nitrogen, argon or the like) isallowed to flow at a constant flow rate during heating, therebyattaining drying, a method in which heating and pressure-reducing iscarried out under reduced pressure, and other methods.

The average particle size of the inorganic substance is usually 1 to5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, andfurther preferably 10 to 100 μm. The pore volume is preferably 0.1 ml/gor more, more preferably 0.3 to 10 ml/g. The specific surface area ispreferably 10 to 1000 m²/g, more preferably 100 to 500 m²/g.

As the organic polymer as the particulate carrier as the component (b4),preferable are polymers having a functional group carrying activehydrogen or a non-proton-donating Lewis basic functional group.

The functional group carrying active hydrogen includes a primary aminogroup, secondary amino group, imino group, amide group, hydrazide group,amidino group, hydroxy group, hydroperoxy group, carboxyl group, formylgroup, carbamoyl group, sulfonic group, sulfinic group, sulfenic group,thiol group, thioformyl group, pyrrolyl group, imidazolyl group,piperidyl group, indazolyl group, carbazolyl group and the like.Preferable is a primary amino group, secondary amino group, imino group,amide group, imide group, hydroxy group, formyl group, carboxyl group,sulfonic group or thiol group. Particularly preferable is a primaryamino group, secondary amino group, amide group or hydroxy group. Thesegroups may have substitution by a halogen atom or a hydrocarbyl grouphaving 1 to 20 carbon atoms.

The non-proton-donating Lewis basic functional group is a functionalgroup having a Lewis base portion having no active hydrogen atom, andincludes a pyridyl group, N-substituted imidazolyl group, N-substitutedindazolyl group, nitrile group, azide group, N-substituted imino group,N,N-substituted amino group, N,N-substituted aminooxy group,N,N,N-substituted hydrazino group, nitroso group, nitro group, nitrooxygroup, furyl group, carbonyl group, thiocarbonyl group, alkoxy group,alkyloxycarbonyl group, N,N-substituted carbamoyl group, thioalkoxygroup, substituted sulfinyl group, substituted sulfonyl group,substituted sulfonic group and the like. Preferable are heterocyclicgroups, and further preferable are aromatic heterocyclic groups havingan oxygen atom and/or nitrogen atom in the ring. Particularly preferableare a pyridyl group, N-substituted imidazolyl group and N-substitutedindazolyl group, and most preferable is a pyridyl group. These groupsmay be substituted by a halogen atom or a hydrocarbyl group having 1 to20 carbon atoms.

In the organic polymer, the content of the functional group carryingactive hydrogen or the non-proton-donating Lewis basic functional groupis preferably 0.01 to 50 mmol/g and more preferably 0.1 to 20 mmol/g, interms of the molar quantity of the functional group per unit gram of apolymer constituting the organic polymer.

As the method of producing a polymer having the functional groupcarrying active hydrogen or the non-proton-donating Lewis basicfunctional group described above, there are mentioned, for example, amethod in which a monomer having the functional group carrying activehydrogen or the non-proton-donating Lewis basic functional group and atleast one polymerizable unsaturated group is homopolymerized, and amethod in which this monomer and other monomer having a polymerizableunsaturated group are copolymerized. In this case, it is preferablethat, further, a crosslink-polymerizable monomer having two or morepolymerizable unsaturated groups is also copolymerized together.

The above-described polymerizable unsaturated group includes alkenylgroups such as a vinyl group, allyl group and the like; alkynyl groupssuch as an ethyne group and the like.

The monomer having the functional group carrying active hydrogen and atleast one polymerizable unsaturated group includes a vinylgroup-containing primary amine, vinyl group-containing secondary amine,vinyl group-containing amide compound, vinyl group-containing hydroxycompound and the like. Specific examples of the monomer includeN-(1-ethenyl)amine, N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine,N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide,N-methyl(1-ethenyl)amide, N-methyl(2-propenyl)amide, vinylalcohol,2-propen-1-ol, 3-buten-1-ol and the like.

The monomer having the functional group having a Lewis base portionhaving no active hydrogen atom and at least one polymerizableunsaturated group includes vinylpyridine, vinyl (N-substituted)imidazole, vinyl (N-substituted) indazole and the like.

Examples of the other monomer having a polymerizable unsaturated groupinclude ethylene, α-olefin, aromatic vinyl compound, cyclic olefin andthe like. Specific examples of the monomer include ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene anddicyclopentadiene. These monomers may be used in combination. Preferableare ethylene and styrene. As the crosslink-polymerizable monomer havingtwo or more polymerizable unsaturated groups, divinylbenzene and thelike are mentioned.

The average particle size of the organic polymer is usually 1 to 5000μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm. The porevolume thereof is preferably 0.1 ml/g or more, and more preferably 0.3to 10 ml/g. The specific surface area thereof is preferably 10 to 1000m²/g, and more preferably 50 to 500 m²/g.

It is preferable that the organic polymer is dried to substantiallyremove water, and those dried by a heating treatment are preferable. Theheating treatment temperature is usually 30 to 400° C., preferably 50 to200° C., further preferably 70 to 150° C., for an organic polymer ofwhich water content cannot be visually confirmed. The heating time ispreferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.The heat dry method includes a method in which a dried inert gas (forexample, nitrogen, argon or the like) is allowed to flow at a constantflow rate during heating, thereby attaining drying, a method in whichdrying with heating is carried out under reduced pressure, and othermethods.

The cocatalyst component (B) is formed by contact of the component (b1),component (b2), component (b3) and component (b4). The order of contactof the component (b1), component (b2), component (b3) and component(b4)) includes the following orders.

<1> The component (b1) and the component (b2) are brought into contact,a contacted substance obtained by this contact and the component (b3)are brought into contact, and a contacted substance obtained by thiscontact and the component (b4) are brought into contact.

<2> The component (b1) and the component (b2) are brought into contact,a contacted substance obtained by this contact and the component (b4)are brought into contact, and a contacted substance obtained by thiscontact and the component (b3) are brought into contact.

<3> The component (b1) and the component (b3) are brought into contact,a contacted substance obtained by this contact and the component (b2)are brought into contact, and a contacted substance obtained by thiscontact and the component (b4) are brought into contact.

<4> The component (b1) and the component (b3) are brought into contact,a contacted substance obtained by this contact and the component (b4)are brought into contact, and a contacted substance obtained by thiscontact and the component (b2) are brought into contact.

<5> The component (b1) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b2)are brought into contact, and a contacted substance obtained by thiscontact and the component (b3) are brought into contact.

<6> The component (b1) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b3)are brought into contact, and a contacted substance obtained by thiscontact and the component (b2) are brought into contact.

<7> The component (b2) and the component (b3) are brought into contact,a contacted substance obtained by this contact and the component (b1)are brought into contact, and a contacted substance obtained by thiscontact and the component (b4) are brought into contact.

<8> The component (b2) and the component (b3) are brought into contact,a contacted substance obtained by this contact and the component (b4)are brought into contact, and a contacted substance obtained by thiscontact and the component (b1) are brought into contact.

<9> The component (b2) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b1)are brought into contact, and a contacted substance obtained by thiscontact and the component (b3) are brought into contact.

<10> The component (b2) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b3)are brought into contact, and a contacted substance obtained by thiscontact and the component (b1) are brought into contact.

<11> The component (b3) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b1)are brought into contact, and a contacted substance obtained by thiscontact and the component (b2) are brought into contact.

<12> The component (b3) and the component (b4) are brought into contact,a contacted substance obtained by this contact and the component (b2)are brought into contact, and a contacted substance obtained by thiscontact and the component (b1) are brought into contact.

Contact with the component (b1), component (b2), component (b3) andcomponent (b4) is preferably carried out under an inert gas atmosphere.The contact temperature is usually −100 to 300° C., preferably −80 to200° C. The contact time is usually 1 minute to 200 hours, preferably 10minutes to 100 hours. A solvent may be used in contact thereof, or thesecompounds may be directly brought into contact using no solvent.

In the case of use of a solvent, those not reacting with the component(b1), component (b2), component (b3) and component (b4) and contactedsubstances thereof are used. However, when the components are broughtinto contact in a stepwise fashion as described above, even a solventreacting with a certain component in a certain stage can be used inother stages providing that it does not react with components in theother stages. That is, solvents in respective stages are mutually thesame or different. Examples of the solvent include nonpolar solventssuch as aliphatic hydrocarbon solvents, aromatic hydrocarbon solventsand the like; and polar solvents such as halide solvents, ethersolvents, alcohol solvents, phenol solvents, carbonyl solvents,phosphoric acid derivatives, nitrile solvents, nitro compounds, aminesolvents, sulfur compounds and the like. Specific examples thereofinclude aliphatic hydrocarbon solvents such as butane, pentane, hexane,heptane, octane, 2,2,4-trimethylpentane, cyclohexane and the like;aromatic hydrocarbon solvents such as benzene, toluene, xylene and thelike; halide solvents such as dichloromethane, difluoromethane,chloroform, 1,2-dichloroethane, 1,2-dibromoethane,1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene,chlorobenzene, bromobenzene, o-dichlorobenzene and the like; ethersolvents such as dimethyl ether, diethyl ether, diisopropyl ether,di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane,1,2-dimethoxyethane, bis(2-methoxyethyl) ether, tetrahydrofuran,tetrahydropyran and the like; alcohol solvents such as methanol,ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzylalcohol,ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol,diethylene glycol, triethylene glycol, glycerin and the like; phenolsolvents such as phenol, p-cresol and the like; carbonyl solvents suchas acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethylacetate, butyl acetate, ethylene carbonate, propylene carbonate,N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone andthe like; phosphoric acid derivatives such as hexamethylphosphorictriamide, triethyl phosphate and the like; nitrile solvents such asacetonitrile, propionitrile, succinonitrile, benzonitrile and the like;nitro compounds such as nitromethane, nitrobenzene and the like; aminesolvents such as pyridine, piperidine, morpholine and the like; sulfurcompounds such as dimethyl sulfoxide, sulfolane and the like.

When a contacted substance (c) obtained by contact of the component(b1), component (b2) and component (b3) is brought into contact with thecomponent (b4), namely in the above-described methods <1>, <3> and <7>,preferable as the solvent (s1) used in the case of production of thecontacted substance (c) are the above-described aliphatic hydrocarbonsolvents, aromatic hydrocarbon solvents and ether solvents.

In contrast, preferable as the solvent (s2) used in the case of contactof the contacted substance (c) and the component (b4) are polarsolvents. As the index showing the polarity of a solvent, E_(T) ^(N)value (C. Reichardt, “Solvents and Solvents Effects in OrganicChemistry”, 2nd ed., VCH Verlag (1988).) and the like are known, andsolvents satisfying the range of 0.8≧E_(T) ^(N)≧0.1 are particularlypreferable.

Examples of such polar solvents include dichloromethane,dichlorodifluoromethanechloroform, 1,2-dichloroethane,1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane,tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene,dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether,methyltert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane,bis(2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran, methanol,ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzylalcohol,ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol,diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone,cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylenecarbonate, propylene carbonate, N,N-dimethylformamide,N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphorictriamide, triethyl phosphate, acetonitrile, propionitrile,succinonitrile, benzonitrile, nitromethane, nitrobenzene,ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide,sulfolane and the like.

The solvent (s2) includes further preferably dimethyl ether, diethylether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether,anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether,tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,3-methyl-1-butanol, cyclohexanol, benzylalcohol, ethylene glycol,propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol,triethylene glycol, particularly preferably , di-n-butyl ether,methyl-tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol,ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, 3-methyl-1-butanol and cyclohexanol, mostpreferably, tetrahydrofuran, methanol, ethanol, 1-propanol and2-propanol.

As the above-described solvent (s2), mixed solvents of these polarsolvents and hydrocarbon solvents can be used. As the hydrocarbonsolvent, compounds exemplified as the aliphatic hydrocarbon solvents andaromatic hydrocarbon solvents are used. Examples of the mixed solventsof polar solvents and hydrocarbon solvents include a hexane/methanolmixed solvent, hexane/ethanol mixed solvent, hexane/1-propanol mixedsolvent, hexane/2-propanol mixed solvent, heptane/methanol mixedsolvent, heptane/ethanol mixed solvent, heptane/1-propanol mixedsolvent, heptane/2-propanol mixed solvent, toluene/methanol mixedsolvent, toluene/ethanol mixed solvent, toluene/1-propanol mixedsolvent, toluene/2-propanol mixed solvent, xylene/methanol mixedsolvent, xylene/ethanol mixed solvent, xylene/1-propanol mixed solvent,xylene/2-propanol mixed solvent and the like. Preferable are ahexane/methanol mixed solvent, hexane/ethanol mixed solvent,heptane/methanol mixed solvent, heptane/ethanol mixed solvent,toluene/methanol mixed solvent, toluene/ethanol mixed solvent,xylene/methanol mixed solvent and xylene/ethanol mixed solvent. Furtherpreferable are a hexane/methanol mixed solvent, hexane/ethanol mixedsolvent, toluene/methanol mixed solvent and toluene/ethanol mixedsolvent. Most preferable is a toluene/ethanol mixed solvent. In atoluene/ethanol mixed solvent, the ethanol fraction is preferably in therange of 10 to 50% by volume, further preferably 15 to 30% by volume.

When a contacted substance (c) obtained by contact of the component(b1), component (b2) and component (b3) is brought into contact with thecomponent (b4), namely in the above-described methods <1>, <3> and <7>,hydrocarbon solvents can also be used as both the solvent (s1) and thesolvent (s2). In this case, it is preferable that time from contact ofthe component (b1), component (b2) and component (b3) until contact ofthe resultant contacted substance (c) and the component (b4) is shorter.This time is preferably 0 to 5 hours, further preferably 0 to 3 hours,and most preferably 0 to 1 hour. The temperature for contact of thecontacted substance (c) and the component (b4) is usually −100° C. to40° C., preferably −20° C. to 20° C., and most preferably −10° C. to 10°C.

In the above-described cases <2>, <5>, <6>, <8>, <9>, <10>, <11> and<12>, any of the above-described nonpolar solvents and polar solventscan be used. The nonpolar solvents are preferable. The reason for thisis believed as follows: since a contacted substance of the component(b1) and the component (b3), and a contacted substance obtained bycontact of a contacted substance of the component (b1) and the component(b2) with the component (b3) are in general poorly soluble in a nonpolarsolvent, when the component (b4) is present in the reaction system inproduction of these contacted substances, the contacted substancesdeposit on the surface of the component (b4), thereby giving fixationtendency thereof.

It is preferable that the use amounts of the component (b2) and thecomponent (b3) per mol of the use amount of the component (b1) satisfythe following relational formula (V).

|atomic valence of M³−molar quantity of component (b2)−2×molar quantityof component (b3)|≦1   (V)

The use amount of the component (b2) per mol of the use amount of thecomponent (b1) is preferably 0.01 to 1.99 mol, more preferably 0.1 to1.8 mol, further preferably 0.2 to 1.5 mol, and most preferably 0.3 to 1mol. The preferable use amount, more preferable use amount, furtherpreferable use amount and most preferable use amount of the component(b3) per mol of the use amount of the component (b1) are calculatedbased on the atomic valence of M³, the use amount of the component (b2)per mol of the use amount of the above-described component (b1) and theabove-described relational formula (V), respectively.

The use amounts of the component (b1) and the component (b2) areregulated so that the amount of metal atoms derived from the component(b1) contained in the component (B) is preferably 0.1 mmol or more, morepreferably 0.5 to 20 mmol, in terms of the mole number of metal atomscontained per g of the cocatalyst component (B).

For progressing the reaction more quickly, a heating process at highertemperature may be added after the contact as described above. In theheating process, it is preferable to use a solvent having higher boilingpoint for attaining higher temperature, and in carrying out the heatingprocess, the solvent used in the contact may be substituted by othersolvent having higher boiling point.

In the cocatalyst component (B), the component (b1), component (b2),component (b3) and/or component (b4) as raw materials may remain asunreacted substances as a result of such contact, however, it ispreferable to previously perform a washing treatment for removingunreacted substances. The solvent used in this procedure may be the sameas or different from the solvent used in the contact. Such a washingtreatment is preferably carried out under an inert gas atmosphere. Thecontact temperature is usually −100 to 300° C., preferably −80 to 200°C. The contact time is usually 1 minute to 200 hours, preferably 10minutes to 100 hours.

After such contact and washing treatment, it is preferable to distilloff the solvent from the product, then, to perform drying at atemperature of 0° C. or higher under reduced pressure for 1 hour to 24hours. It is carried out more preferably at a temperature of 0° C. to200° C. for 1 hour to 24 hours, further preferably at a temperature of10° C. to 200° C. for 1 hour to 24 hours, particularly preferably at atemperature of 10° C. to 160° C. for 2 hours to 18 hours, and mostpreferably at a temperature of 15° C. to 160° C. for 4 hours to 18hours.

To total use amount of the transition metal compound (A1) and thetransition metal compound (A2) is usually 1 to 10000 μmol/g, preferably10 to 1000 μmol/g, and more preferably 20 to 500 μmol/g, per g of thecocatalyst component (B).

In preparation of the polymerization catalyst, an organoaluminumcompound (C) may also be contacted, in addition to the transition metalcompound (A1), the transition metal compound (A2) and the cocatalystcomponent (B). The use amount of the organoaluminum compound (C) ispreferably 0.1 to 1000, more preferably 0.5 to 500 and furtherpreferably 1 to 100, in terms of mole number of aluminum atoms in theorganoaluminum compound (C) per mol of the sum of the transition metalcompound (A1) and the transition metal compound (A2).

The organoaluminum compound (C) includes trialkylaluminums such astrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like; dialkylaluminum chlorides such asdimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminumchloride, di-n-butylaluminum chloride, diisobutylaluminum chloride,di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides suchas methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminumdichloride, n-butylaluminum dichloride, isobutylaluminum dichloride,n-hexylaluminum dichloride and the like; dialkylaluminum hydrides suchas dimethylaluminum hydride, diethylaluminum hydride,di-n-propylaluminum hydride, di-n-butylaluminum hydride,diisobutylaluminum hydride, di-n-hexylaluminum hydride and the like;alkyl(dialkoxy)aluminums such as methyl(dimethoxy)aluminum,methyl(diethoxy)aluminum, methyl(di-tert-butoxy)aluminum and the like;dialkyl(alkoxy)aluminums such as dimethyl(methoxy)aluminum,dimethyl(ethoxy)aluminum, methyl(tert-butoxy)aluminum and the like;alkyl(diaryloxy)aluminums such as methyl(diphenoxy)aluminum, methylbis(2,6-diisopropylphenoxy)aluminum, methylbis(2,6-diphenylphenoxy)aluminumand the like; dialkyl(aryloxy)aluminums such asdimethyl(phenoxy)aluminum, dimethyl(2,6-diisopropylphenoxy)aluminum,dimethyl(2,6-diphenylphenoxy)aluminum and the like; etc. Theseorganoaluminum compounds may be used singly or in combination of two ormore.

The organoaluminum compound (C) is preferably a trialkylaluminum, morepreferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, furtherpreferably triisobutylaluminum or tri-n-octylaluminum.

In preparation of the polymerization catalyst, an electron donativecompound (D) may be brought into contact, in addition to the transitionmetal compound (A1), the transition metal compound (A2) and thecocatalyst component (B). The use amount of the electron donativecompound (D) is preferably 0.01 to 100, more preferably 0.1 to 50 andfurther preferably 0.25 to 5, in terms of the mole number of theelectron donative compound (D) per mol the sum of the transition metalcompound (A1) and the transition metal compound (A2)

The electron donative compound (D) includes triethylamine andtri-n-octylamine.

Contact of the transition metal compound (A1), the transition metalcompound (A2) and the cocatalyst component (B), and if necessary, theorganoaluminum compound (C) and the electron donative compound (D), ispreferably carried out under an inert gas atmosphere. The contacttemperature is usually −100 to 300° C., preferably −80 to 200° C. Thecontact time is usually 1 minute to 200 hours, preferably 30 minutes to100 hours. It may also be permissible that components are separatelycharged into polymerization reaction tanks, and brought into contact ina polymerization reaction vessel.

The method of producing the ethylene-α-olefin copolymer of the presentinvention includes methods of copolymerizing ethylene and an α-olefin bya gas phase polymerization method, slurry polymerization method, bulkpolymerization method and the like. A gas phase polymerization method ispreferable, and a continuous gas phase polymerization method is morepreferable. The gas phase polymerization reaction apparatus to be usedin the polymerization method is usually an apparatus having a fluidizedbed type reaction tank, and preferably an apparatus having a fluidizedbed type reaction tank having an enlarged part. A stirring blade mayalso be installed in the reaction tank.

As the method of feeding the polymerization catalyst and variouscatalyst components to a polymerization reaction bath, a method offeeding under anhydrous state using an inert gas such as nitrogen, argonand the like, and hydrogen, ethylene and the like, and a method in whichcomponents are dissolved in or diluted with a solvent and fed in theform of solution or slurry, are usually used.

In the case of gas phase polymerization of ethylene and an α-olefin, thepolymerization temperature is usually lower than the temperature atwhich the ethylene-α-olefin copolymer is melted, and preferably 0 to150° C., more preferably 30 to 100° C. In the polymerization reactiontank, an inert gas may be introduced, and hydrogen may be introduced asa molecular weight modifier. Further, an organoaluminum compound (C) andan electron donative compound (D) may also be introduced.

The α-olefin to be used for polymerization include α-olefins having 3 to20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene,4-methyl-1-hexene and the like. These may be used singly or incombination of two or more. Preferable are 1-butene, 1-hexene,4-methyl-1-pentene and 1-octene. The combination of ethylene and anα-olefin includes ethylene/1-butene, ethylene/1-hexene,ethylene/4-methyl-1-pentene, ethylene/1-octene,ethylene/1-butene/1-hexene, ethylene/1-butene/4-methyl-1-pentene,ethylene/1-butene/1-octene, ethylene/1-hexene/1-octene and the like,preferably ethylene/1-hexene, ethylene/4-methyl-1-pentene,ethylene/1-butene/1-hexene, ethylene/1-butene/1-octene andethylene/1-hexene/1-octene.

In copolymerization of ethylene and an α-olefin, if necessary, othermonomers may be introduced into a polymerization reaction tank, and maybe copolymerized in the range not deteriorating the effect of thepresent invention. The other monomers include a diolefin, cyclic olefin,alkenylaromatic hydrocarbon, α,β-unsaturated carboxylic acid and thelike.

Specific examples thereof include diolefins such as 1,5-hexadiene,1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene,5-methylene-2-norbornene, 1,5-cyclooctadiene,5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene,1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene andthe like; cyclic olefins such as cyclopentene, cyclohexene, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene,5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene,tricyclodecene, tricycloundecene, pentacyclopentadecene,pentacyclohexadecene, 8-methyltetracyclododecene,8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene,5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene,5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene,8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene,8-cyanotetracyclododecene and the like; alkenylaromatic hydrocarbonssuch as alkenylbenzenes such as styrene, 2-phenylpropylene,2-phenylbutene, 3-phenylpropylene and the like, alkylstyrenes such asp-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene,m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene,2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene,3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-secondarybutylstyrene and the like, bisalkenylbenzenes such as divinylbenzene andthe like, alkenylnaphthalenes such as 1-vinylnaphthalene and the like;α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid,fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride,bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid and the like; salts ofα,β-unsaturated carboxylic acids with a metal such as sodium, potassium,lithium, zinc, magnesium, calcium and the like; α,β-unsaturatedcarboxylic acid alkyl esters such as methyl acrylate, ethyl acrylate,n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutylmethacrylate and the like; unsaturated dicarboxylic acids such as maleicacid, itaconic acid and the like; vinyl esters such as vinyl acetate,vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinylstearate, vinyl trifluoroacetate and the like; unsaturated carboxylicacid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate,itaconic acid monoglycidyl ester and the like; etc.

As the method of producing the ethylene-α-olefin copolymer of thepresent invention, preferable is a method of copolymerizing ethylene andan α-olefin with use, as a polymerization catalyst component orpolymerization catalyst, of a prepolymerized solid component obtained bypolymerizing a small amount of olefin (hereinafter, referred to asprepolymerization), using the transition metal compound (A1) and thetransition metal compound (A2) and the cocatalyst component (B), and ifnecessary, further, the organoaluminum compound (C) and the electrondonating compound (D).

The olefin to be used in prepolymerization includes ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene,cyclopentene, cyclohexene and the like. These can be used singly or incombination of two or more. Preferably, ethylene is singly used orethylene and an α-olefin are used together, further preferably, ethyleneis singly used or ethylene and at least one α-olefin selected from1-butene, 1-hexene and 1-octene are used together.

The content of the prepolymerized polymer in the prepolymerized solidcomponent is preferably 0.01 to 1000 g, more preferably 0.05 to 500 gand further preferably 0.1 to 200 g per gram of the co-catalystcomponent (B).

The method of prepolymerization may be continuous or batch-wise, andexamples thereof include a batch-wise slurry polymerization method,continuous slurry polymerization method and continuous gas phasepolymerization method. As the method of charging the transition metalcompound (A1) and the transition metal compound (A2) and the cocatalystcomponent (B), and if necessary, further, the organoaluminum compound(C) and the electron donating compound (D) into a polymerizationreaction tank for carrying out prepolymerization, a method of chargingunder anhydrous state using an inert gas such as nitrogen, argon and thelike, and hydrogen, ethylene and the like, and a method in whichcomponents are dissolved in or diluted with a solvent and charged in theform of solution or slurry, are usually used.

In the case of conducting prepolymerization by a slurry polymerizationmethod, saturated aliphatic hydrocarbon compounds are usually used asthe solvent, and examples thereof include propane, n-butane, isobutane,n-pentane, isopentane, n-hexane, cyclohexane, heptane and the like.These are used singly or in combination of two or more. As the saturatedaliphatic hydrocarbon compound, those having a boiling point at normalpressure of 100° C. or less are preferable, those having a boiling pointat normal pressure of 90° C. or less are more preferable, and propane,n-butane, isobutane, n-pentane, isopentane, n-hexane and cyclohexane arefurther preferable.

In the case of conducting prepolymerization by a slurry polymerizationmethod, the slurry concentration is usually 0.1 to 600 g, preferably 0.5to 300 g, in terms of the amount of the cocatalyst component (B) perliter of a solvent. The prepolymerization temperature is usually −20 to100° C., preferably 0 to 80° C. During prepolymerization, thepolymerization temperature may be changed appropriately. The partialpressure of olefins in a gas phase portion during prepolymerization isusually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerizationtime is usually 2 minutes to 15 hours.

As the method of feeding the prepolymerized solid catalyst componentwhich has been prepolymerized to a polymerization reaction tank, amethod of charging under anhydrous state using an inert gas such asnitrogen, argon and the like, and hydrogen, ethylene and the like, and amethod in which components are dissolved in or diluted with a solventand charged in the form of solution or slurry, are usually used.

The ethylene-α-olefin copolymer of the present invention may be allowedto contain known additives, if necessary. Examples of the additiveinclude an antioxidant, anti-weathering agent, lubricant, anti-blockingagent, anti-static agent, anti-fogging agent, anti-dropping agent,pigment, filler and the like.

The ethylene-α-olefin copolymer of the present invention is molded byknown molding methods, for example, extrusion molding methods, hollowmolding methods and injection molding methods such as a blown filmmolding method, flat die film molding method and the like; compressionmolding methods, and the like. As the molding method, extrusion moldingmethods and follow molding methods are suitably used, and extrusionmolding methods are more suitably used, and a flat die film moldingmethod is particularly suitably used.

The ethylene-α-olefin copolymer of the present invention is molded intovarious forms and used. The form of a molded article is not particularlyrestricted, and it is used in the form of a film, sheet, vessel (tray,bottle or the like) and the like. The molded article is suitably usedalso in applications such as food packaging materials; medical articlepackaging materials; electronic parts packaging materials used forpackaging of semiconductor products and the like; surface protectivematerials, and the like.

As described above, the ethylene-α-olefin copolymer of the presentinvention is excellent in extrusion load, swell ratio and mechanicalstrength in molding processing. Thus, neck-in in molding a flat die filmcan also be lowered. Further, taking-up property in extrusion molding isalso excellent.

The ethylene-α-olefin copolymer of the present invention can also beblended in suitable amount in a conventional ethylenic polymer, for thepurpose of improving neck-in of an ethylenic polymer poor in neck-in.For example, neck-in can be significantly improved by blending theethylene-α-olefin copolymer of the present invention in suitable amountin an ethylenic polymer such as a linear low density polyethylene andthe like.

The present invention will be illustrated by examples and comparativeexamples below.

In the examples and the comparative examples, physical properties weremeasured according to the following methods.

(1) Density (d, Unit: kg/m³)

The density was measured according to a method defined in method A ofJIS K7112-1980. A sample was subjected to annealing described in JISK6760-1995.

(2) Melt Flow Rate (MFR, Unit: g/10 minutes)

The melt flow rate was measured by method A under conditions of a loadof 21.18 N and a temperature of 190° C. according to a method defined inJIS K7210-1995.

(3) Melt Flow Rate Ratio (MFRR)

The melt flow rate (H-MFR) was measured under conditions of a test loadof 211.82 N and a measurement temperature of 190° C. in a method definedin JIS K7210-1995 and the melt flow rate (MFR) was measured underconditions of a load of 21.18 N and a temperature of 190° C. in a methoddefined in JIS K7210-1995, and H-MFR was divided by MFR to give a valueof the melt flow rate ratio.

(4) Swell Ratio (SR)

A strand of an ethylene-α-olefin copolymer extruded with a length ofabout 15 to 20 mm from an orifice under conditions of a temperature of190° C. and a load of 21.18 N, in measurement of the melt flow rate (2),was cooled in air to obtain a strand in solid state. Then, the diameterD (unit: mm) of the strand was measured at a position about 5 mm fromthe end at the extrusion upstream side of the strand and the diameter Dwas divided by the orifice diameter: 2.095 mm (D₀), to give a value(D/D₀) of the swell ratio.

(5) Molecular Weight Distribution (Mw/Mn, Mz/Mw)

The z average molecular weight (Mz), weight average molecular weight(Mw) and number average molecular weight (Mn) were measured using a gelpermeation chromatograph (GPC) method, under the following conditions(1) to (8), and Mw/Mn and Mz/Mw were calculated. The base line on thechromatogram was a straight line obtained by connecting a point instable horizontal region of sufficiently shorter retention time thanemergence of sample elution peak and a point in stable horizontal regionof sufficiently longer retention time than observation of solventelution peak.

(1) Apparatus: Waters 150 C manufactured by Waters

(2) Separation column: TOSOH TSkgel GMH6-HT

(3) Measuring temperature: 140° C.

(4) Carrier: orthodichlorobenzene

(5) Flow rate: 1.0 mL/min

(6) Injection volume: 500 μL

(7) Detector: differential refraction

(8) Molecular weight reference material: standard polystyrene

(6) The Number of Branches having 5 or more Carbon Atoms (N_(LCB), Unit:1/1000C)

A carbon nuclear magnetic resonance spectrum (¹³C-NMR) was measured by acarbon nuclear magnetic resonance method under the following measurementconditions, and the number of branches was obtained according to thefollowing calculation method.

<Measurement Conditions>

Apparatus: AVANCE600 manufactured by Bruker

Measurement solvent: mixed liquid of1,2-dichlorobenzene/1,2-dichlorobenzene-d4=75/25 (ratio by volume)

Measurement temperature: 130° C.

Measurement method: proton de-coupling method

Pulse width: 45°

Pulse repetition time: 4 seconds

Measurement standard: trimethylsilane

Window function: negative exponential function

<Calculation Method>

The peak area of a peak was measured having a peak top around 38.22 to38.27 ppm, the sum of all peaks observed in 5 to 50 ppm being 1000. Thepeak area of the peak was the area of signals in a range from a chemicalshift at a valley of a peak adjacent at the higher magnetic field sideand a chemical shift at a valley of a peak adjacent at the lowermagnetic field side. In measurement of an ethylene-1-octene copolymerunder this condition, the position of a top of a peak ascribable to amethine carbon to which a branch having 6 carbon atoms had beenconnected was 38.21 ppm.

(7) Number of Short Chain Branch (N_(SCB), Unit: 1/1000C)

The number of short chain branches in an ethylene-α-olefin copolymer wasmeasured by an infrared absorption spectrum. The measurement andcalculation were carried out utilizing the characteristic absorptionderived from an α-olefin, according to a method described in aliterature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, M. A.,Madams, W. F.). The infrared absorption spectrum was measured using aninfrared spectrophotometer (FT-IR7300, manufactured by JASCOCorporation)

(8) g*

g* was calculated according to the above-described formula (II).

An ethylene-α-olefin copolymer (100 mg) was dissolved at 135° C. in 100ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) asa thermal degradation inhibitor to prepare a sample solution, and therelative viscosity (ηrel) of the ethylene-α-olefin copolymer wascalculated from the fall time of the above-described sample solution andthe fall time of a blank solution composed of tetralin containing only0.5% by weight of BHT as a thermal degradation inhibitor obtained byusing a Ubbelohde type viscometer, and [η] was calculated according tothe formula (II-I), and [η]_(GPC) was calculated according to theformula (II-II) from measurement of the molecular weight distribution ofthe ethylene-α-olefin copolymer of the item (5), and g_(SCB)* wascalculated according to the formula (II-III) from measurement of thenumber of short chain branches in the ethylene-α-olefin copolymer of theitem (7).

(9) Melt Complex Viscosity (η*, Unit: Pa·sec)

A melt complex viscosity-angular frequency curve at 190° C. was measuredunder the following measurement conditions using a viscoelasticitymeasurement apparatus (Rheometrics Mechanical Spectrometer RMS-800manufactured by Rheometrics), and the melt complex viscosity measured atan angular frequency of 100 rad/second was obtained. Lower the meltcomplex viscosity, more excellent the extrusion load in extrusionmolding.

<Measurement Conditions>

geometry: parallel plate

plate diameter: 25 mm

plate interval: 1.5 to 2 mm

strain: 5%

angular frequency: 0.1 to 100 rad/second

measurement atmosphere: nitrogen

(10) Maximum Take-Up Velocity (MTV, Unit: m/min)

Using a melt tension tester manufactured by Toyo Seiki Seisaku-sho Ltd.,an ethylene-α-olefin copolymer was melt-extruded from an orifice havinga diameter of 2.095 mm and a length of 8 mm at a temperature of 150° C.and an extrusion speed of 0.32 g/min, and the extruded moltenethylene-α-olefin copolymer was taken up in the form of a filament at atake-up rising speed of 6.3 (m/min)/min by a take-up roll. The take-upspeed in breaking of the filamentous ethylene-α-olefin copolymer was themaximum take-up velocity. Higher this value, more excellent thetaking-up property in extrusion molding.

(11) Impact Strength (Unit: kJ/m²)

The impact strength was measured according to ASTM D1822-68.

(12) Characteristic Relaxation Time (τ, Unit: Second)

Using a viscoelasticity measurement apparatus (Rheometrics MechanicalSpectrometer RMS-800 manufactured by Rheometrics), melt complexviscosity-angular frequency curves at 130° C., 150° C., 170° C. and 190°C. were measured under the following measurement conditions, next, amaster curve of the melt complex viscosity-angular frequency curve at190° C. was made from the resultant melt complex viscosity-angularfrequency curves using a calculation software Rhios V.4.4.4 availablefrom Rheometrics, and the characteristic relaxation time (τ) wasdetermined.

<Measurement Conditions>

geometry: parallel plate

plate diameter: 25 mm

plate interval: 1.5 to 2 mm

strain: 5%

angular frequency: 0.1 to 100 rad/second

measurement atmosphere: nitrogen

(13) Flow Activation Energy (Ea, Unit: kJ/mol)

Using a viscoelasticity measurement apparatus (Rheometrics MechanicalSpectrometer RMS-800 manufactured by Rheometrics), melt complexviscosity-angular frequency curves at 130° C., 150° C., 170° C. and 190°C. were measured under the following measurement conditions, next, amaster curve of the melt complex viscosity-angular frequency curve at190° C. was made from the resultant melt complex viscosity-angularfrequency curves using a calculation software Rhios V.4.4.4 availablefrom Rheometrics, and the activation energy (Ea) was determined.

<Measurement Conditions>

geometry: parallel plate

plate diameter: 25 mm

plate interval: 1.5 to 2 mm

strain: 5%

angular frequency: 0.1 to 100 rad/second

measurement atmosphere: nitrogen

EXAMPLE 1 (1) Preparation of Solid Catalyst Component

Into a nitrogen-purged reaction vessel equipped with a stirring devicewas charged 24 kg of toluene and 2.8 kg of silica (Sylopol948manufactured by Davison; 50% volume average particle size=55 μm; porevolume=1.67 ml/g; specific surface area=325 m²/g) which had beenheat-treated at 300° C. under nitrogen flow, and the mixture wasstirred. Thereafter, the mixture was cooled to 5° C., then, a mixedsolution composed of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4kg of toluene was dropped over a period of 30 minutes while keeping thetemperature of the reaction vessel at 5° C. After completion ofdropping, the mixture was stirred at 5° C. for 1 hour, next, heated upto 95° C., and stirred at 95° C. for 3 hours, and filtrated. Theresultant solid product was washed with 20.8 kg of toluene six times.Thereafter, 7.1 kg of toluene was added to give a slurry which was thenallowed to stand still overnight.

To the slurry obtained above, 1.73 kg of a hexane solution ofdiethylzinc (diethylzinc concentration: 50% by weight) and 1.02 kg ofhexane were added, and the mixture was stirred. Thereafter, the mixturewas cooled to 5° C., then, a mixed solution composed of 0.78 kg of3,4,5-trifluorophenol and 1.44 kg of toluene was dropped over a periodof 60 minutes while keeping the temperature of the reaction vessel at 5°C. After completion of dropping, the mixture was stirred at 5° C. for 1hour, then, heated up to 40° C. and stirred at 40° C. for 1 hour.Thereafter, the mixture was cooled to 22° C., and 0.11 kg of H₂O wasdropped over a period of 1.5 hours while keeping the temperature of thereaction vessel at 22° C. After completion of dropping, the mixture wasstirred at 22° C. for 1.5 hours, then, heated up to 40° C. and stirredat 40° C. for 2 hours, and further heated up to 80° C. and stirred at80° C. for 2 hours. After stirring, the supernatant was extracted to aresidual amount of 16 L at room temperature, 11.6 kg of toluene wasadded, then, the mixture was heated up to 95° C. and stirred for 4hours. After stirring, the supernatant was extracted at room temperatureto obtain a solid product. The resultant solid product was washed with20.8 kg of toluene four times and with 24 liters of hexane three times.Thereafter, the product was dried to obtain a solid catalyst component.

(2) Preparation of Prepolymerized Catalyst Component

Into a previously nitrogen-purged autoclave equipped with a stirringdevice having an internal volume of 5 liters was added 835 g of butane,then, the autoclave was heated up to 50° C., and 60 mg ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] and 0.68 g ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)] were added in the form of a powder, andthe mixture was stirred at 50° C. for 75 minutes. Next, 28 g of ethylenewas charged, and after stabilization in the system, 10.6 g of the solidcatalyst component obtained in Example 1(1) was added, subsequently, 4.2ml of a heptane solution of triisobutylaluminum having atriisobutylaluminum concentration of 1 mmol/ml was added, andpolymerization was initiated. Prepolymerization was carried out at 50°C. for 100 minutes while continuously feeding a mixed gas of ethyleneand hydrogen having a hydrogen concentration of 0.2%. After completionof polymerization, ethylene, butane, hydrogen and the like were purgedto give a residual solid which was then dried at room temperature, toobtain a prepolymerized catalyst component containing 16.5 g ofpolyethylene per gram of the solid catalyst component.

(3) Polymerization

An atmosphere in a 5 L autoclave equipped with a stirring device whichhad been purged with argon after drying under reduced pressure wasevacuated, and hydrogen was added so that its partial pressure was 0.051MPa, and 200 ml of 1-hexene and 1065 g of butane were charged, and thetemperature in the system was raised up to 70° C., then, ethylene wasintroduced so that its partial pressure was 1.6 MPa, to attainstabilization in the system. As a result of gas chromatography, the gascomposition in the system contained hydrogen=2.65 mol %. To this wasadded 1.0 ml of a toluene solution of triethylamine having atriethylamine concentration of 0.1 mmol/ml, then, 2.0 ml of a heptanessolution of triisobutylaluminum having a triisobutylaluminumconcentration of 1 mmol/ml was added. Next, 355 mg of the prepolymerizedcatalyst component obtained in Example 1(2) was added. Polymerizationwas carried out at 70° C. for 220 minutes while continuously feeding anethylene/hydrogen mixed gas (hydrogen=0.49 mol %) so that the totalpressure and the hydrogen concentration in the gas were maintainedconstant during polymerization. Thereafter, butane, ethylene andhydrogen were purged, to obtain 117 g of an ethylene-1-hexene copolymer.The physical properties of the resultant copolymer are shown in Table 1.

EXAMPLE 2 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.03 MPa, and 180 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=1.84 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.5 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.8 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 38.7 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.25 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 182 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 3 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.04 MPa, and 200 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=2.21 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.3 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.5 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 16.4 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.25 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 101 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 4 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.04 MPa, and 180 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=2.12 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.5 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.8 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 29.2 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.27 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 189 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 5 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.04 MPa, and 160 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=2.52 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.5 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.8 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 20.6 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.25 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 135 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 6 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.06 MPa, and 180 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=3.56 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.5 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.8 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 23.1 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.29 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 118 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 7 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.08 MPa, and 180 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=4.99 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.3 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.3 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 1 μmol/ml were added, subsequently, 31.8 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.31 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 97.1 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 8 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.04 MPa, and 180 ml of 1-hexene and 650 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=2.41 mol %. To this was added 0.9 ml of a hexanesolution of triisobutylaluminum having a concentration adjusted to 1mol/l as the organoaluminum compound (C). Next, 0.45 ml of a toluenesolution of racemic-ethylenebis(1-indenyl)zirconium diphenoxide[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 0.3 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 9.9 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.25 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 124.4 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 9 (1) Preparation of Prepolymerized Catalyst Component

Into a previously nitrogen-purged autoclave equipped with a stirringdevice having an internal volume of 5 liters was added 833 g of butane,then, the autoclave was heated up to 50° C., then, 28 g of ethylene wascharged, to attain stabilization in the system. Next, separately in a 50ml flask, 57 mg ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)], 0.67 g ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)], and 4.1 ml of a hexane solution oftriisobutylaluminum having a triisobutylaluminum concentration of 1mmol/ml as the organoaluminum compound (C) were mixed and stirred to mixat 50° C. for 4 hours under a nitrogen atmosphere, and the resultantsolution was placed in an autoclave. Subsequently, 10.4 g of the solidcatalyst component prepared in Example 1 was added, and polymerizationwas initiated. Prepolymerization was carried out at 50° C. for 80minutes while continuously feeding a mixed gas of ethylene and hydrogenhaving a hydrogen concentration of 0.2%. After completion ofpolymerization, ethylene, butane, hydrogen and the like were purged togive a residual solid which was then dried at room temperature, toobtain a prepolymerized catalyst component containing 17.5 g ofpolyethylene per gram of the solid catalyst component.

(2) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.035 MPa, and 180 ml of 1-hexene and 650g of butane were charged, and the temperature in the system raised up to70° C., then, ethylene was added so that its partial pressure was 1.6MPa, to attain stabilization in the system. As a result of gaschromatography, the gas composition in the system containedhydrogen=2.15 mol %. To this was added 0.9 ml of a hexane solution oftriisobutylaluminum having a triisobutylaluminum concentration of 1mmol/ml as the organoaluminum compound (C). Next, 363 mg of theprepolymerized catalyst component obtained in Example 9(1) was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.24 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 128 g of anethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 10 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.028 MPa, and 55 g of 1-butene and 695 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=1.34 mol % and 1-butene=2.31 mol %. To this was added0.9 ml of a hexane solution of triisobutylaluminum having aconcentration adjusted to 1 mol/l as the organoaluminum compound (C).Next, 0.5 ml of a toluene solution ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)] having a concentration adjusted to 2μmol/ml and 1 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 10.1 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.38 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 105 g of anethylene-1-butene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 11 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.058 MPa, and 45 g of 1-butene and 705 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=3.21 mol % and 1-butene=2.82 mol %. To this was added0.9 ml of a hexane solution of triisobutylaluminum having aconcentration adjusted to 1 mol/l as the organoaluminum compound (C).Next, 0.5 ml of a toluene solution ofracemic-dimethylsilylenebis(1-indenyl)zirconium dichloride[corresponding to transition metal compound (A1)] having a concentrationadjusted to 2 μmol/ml and 1.0 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 0.1 μmol/ml were added, subsequently, 8.9 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.77 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 85 g of anethylene-1-butene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 12 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.03 MPa, and 120 ml of 1-hexene and 650 gof butane were charged, and the temperature in the system was raised upto 70° C., then, ethylene was added so that its partial pressure was 1.0MPa, to attain stabilization in the system. As a result of gaschromatography, the gas composition in the system containedhydrogen=2.37 mol %. To this was added 0.9 ml of a hexane solution oftriisobutylaluminum having a triisobutylaluminum concentration of 1mmol/ml as the organoaluminum compound (C). Next, 289 mg of theprepolymerized catalyst component obtained in Example 9(1) describedabove was added. Polymerization was carried out at 70° C. for 120minutes while continuously feeding an ethylene/hydrogen mixed gas(hydrogen=0.24 mol %) so that the total pressure and the hydrogenconcentration in the gas were maintained constant during polymerization.Thereafter, butane, ethylene and hydrogen were purged, to obtain 79 g ofan ethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

EXAMPLE 13 (1) Preparation of Prepolymerized Catalyst Component

Into a previously nitrogen-purged autoclave equipped with a stirringdevice having an internal volume of 5 liters was added 836 g of butane,then, the autoclave was heated up to 50° C., then, 28 g of ethylene wascharged, to attain stabilization in the system. Next, separately in a 50ml flask, 0.25 g ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)], 0.52 g ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)], and 4.3 ml of a hexane solution oftriisobutylaluminum having a triisobutylaluminum concentration of 1mmol/ml were mixed and stirred to mix at 50° C. for 4 hours under anitrogen atmosphere, and the resultant solution was placed in anautoclave. Then, further, 10.3 g of the solid catalyst componentobtained in Example 1(1) was added, and polymerization was initiated.Prepolymerization was carried out at 50° C. for 100 minutes whilecontinuously feeding a mixed gas of ethylene and hydrogen having ahydrogen concentration of 0.2%. After completion of polymerization,ethylene, butane, hydrogen and the like were purged to give a residualsolid which was then dried at room temperature, to obtain aprepolymerized catalyst component containing 15.9 g of polyethylene pergram of the solid catalyst component.

(2) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.08 MPa, and 180 ml of 1-hexene and 650 gof butane were charged, and the temperature in the system raised up to70° C., then, ethylene was added so that its partial pressure was 1.6MPa, to attain stabilization in the system. As a result of gaschromatography, the gas composition in the system containedhydrogen=4.73 mol %. To this was added 0.9 ml of a hexane solution oftriisobutylaluminum having a triisobutylaluminum concentration of 1mmol/ml as the organoaluminum compound (C). Next, 333 mg of theprepolymerized catalyst component obtained in Example 13(1) describedabove was added. Polymerization was carried out at 70° C. for 120minutes while continuously feeding an ethylene/hydrogen mixed gas(hydrogen=0.33 mol %) so that the total pressure and the hydrogenconcentration in the gas were maintained constant during polymerization.Thereafter, butane, ethylene and hydrogen were purged, to obtain 78 g ofan ethylene-1-hexene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

COMPARATIVE EXAMPLE 1 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.065 MPa, and 50 g of 1-butene and 700 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=3.69 mol % and 1-butene=2.09 mol %. To this was added0.9 ml of a hexane solution of triisobutylaluminum having aconcentration adjusted to 1 mmol/ml as the organoaluminum compound (C).Next, 0.5 ml of a toluene solution ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)] having a concentration adjusted to 2μmol/ml and 0.5 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 2 μmol/ml were added, subsequently, 21.8 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.58 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 85 g of anethylene-1-butene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

COMPARATIVE EXAMPLE 2 (1) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.08 MPa, and 55 g of 1-butene and 695 gof butane as a polymerization solvent were charged, and the temperaturewas raised up to 70° C. Then, ethylene was added so that its partialpressure was 1.6 MPa, to attain stabilization in the system. As a resultof gas chromatography analysis, the gas composition in the systemcontained hydrogen=3.68 mol % and 1-butene=2.22 mol %. To this was added0.9 ml of a hexane solution of triisobutylaluminum having aconcentration adjusted to 1 mol/l as the organoaluminum compound (C).Next, 0.5 ml of a toluene solution ofracemic-ethylenebis(1-indenyl)zirconium diphenoxide [corresponding totransition metal compound (A1)] having a concentration adjusted to 2μmol/ml and 1.0 ml of a toluene solution ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride[corresponding to transition metal compound (A2)] having a concentrationadjusted to 2 μmol/ml were added, subsequently, 31.3 mg of the solidcatalyst component obtained in Example 1(1) described above was added.Polymerization was carried out at 70° C. for 60 minutes whilecontinuously feeding an ethylene/hydrogen mixed gas (hydrogen=0.80 mol%) so that the total pressure and the hydrogen concentration in the gaswere maintained constant during polymerization. Thereafter, butane,ethylene and hydrogen were purged, to obtain 121 g of anethylene-1-butene copolymer. The physical properties of the resultantcopolymer are shown in Table 1.

COMPARATIVE EXAMPLE 3 (1) Production of Modified Particle

Into a nitrogen-purged 5 L four-necked flask was charged 2 liters oftetrahydrofuran and 1.35 liters (2.7 mol) of a hexane solution (2M) ofdiethylzinc, and the mixture was cooled to −50° C. Into this, a solutionprepared by dissolving 251.5 g (1.37 mol) of pentafluorophenol in 390 mlof tetrahydrofuran was dropped over a period of 25 minutes. Aftercompletion of dropping, the temperature was gradually raised up to roomtemperature, and the mixture was stirred for 3 hours. Thereafter, themixture was heated at 45° C. and stirred for 1 hour. The temperature waslowered down to 20° C. with an ice bath, and 37.72 g (2.09 mol) of H₂Owas dropped over a period of 1.4 hours. As a result, the mixture wasseparated into a yellow transparent liquid substance and a yellow gelledsubstance. After completion of dropping, the mixture was stirred for 2hours, heated up to 40° C., then, further stirred for 1 hour. Themixture was allowed to stand still overnight at room temperature, then,72% by weight of the yellow transparent liquid substance and the totalamount of the yellow gelled substance were separated into separateflasks which had been purged with nitrogen, and volatile components weredistilled off respectively, and dried at 120° C. for 8 hours underreduced pressure. Thereafter, a solid derived from the yellowtransparent liquid substance was dissolved in 3 liters oftetrahydrofuran, and this was transferred into a 5 L flask containing asolid derived from the yellow gelled substance. This was allowed tostand still for 69 hours at room temperature, then, dried under reducedpressure at 120° C. for 8 hours. As a result, 374 g of a solid productwas obtained.

Into a nitrogen-purged 5 L four-necked flask was charged 374 g of theabove-described solid product and 3 liters of tetrahydrofuran, and themixture was stirred. To this was added 282 g of silica (Sylopol948manufactured by Davison; average particle size=61 μm; pore volume=1.61ml/g; specific surface area=296 m²/g) which had been heat-treated at300° C. under nitrogen flow. The mixture was heated at 40° C. andstirred for 2 hours, then, a solid component was allowed to deposit, anda slurry portion of the upper layer was removed. As a washing operation,to this was added 3 liters of tetrahydrofuran and the mixture wasstirred, then, a solid component was allowed to deposit, and a slurryportion of the upper layer was removed. The above-described washingoperation was repeated five times in total. After removing a liquidcomponent by a grass filter, drying was carried out at 120° C. for 8hours under reduced pressure, to obtain 452 g of modified particles.

(2) Polymerization

An atmosphere in an autoclave equipped with a stirring device having aninternal volume of 3 liters which had been purged with argon afterdrying under reduced pressure was evacuated, and hydrogen was added sothat its partial pressure was 0.001 MPa, and 680 g of butane and 70 g of1-butene were charged, and the temperature was raised up to 70° C. Then,ethylene was added so that its partial pressure was 1.6 MPa, to attainstabilization in the system. As a result of gas chromatography analysis,the gas composition in the system contained hydrogen=0.04 mol % and1-butene=3.21 mol %. To this was added 0.9 ml of a heptane solution oftriisobutylaluminum having a concentration adjusted to 1 mmol/ml as theorganoaluminum compound (C). Next, 7.9 ml of a mixed toluene solutioncontaining three transition metal compounds having aracemic-ethylenebis(1-indenyl)hafnium dichloride concentration adjustedto 0.84 μmol/ml, a racemic-ethylenebis(1-indenyl)zirconium dichlorideconcentration adjusted to 0.06 μmol/ml and abis(n-butylcyclopentadienyl)zirconium dichloride concentration adjustedto 0.25 μmol/ml was added, subsequently, 14.0 mg of the modifiedparticles obtained in Comparative Example 4(1) described above wereadded as the solid catalyst component. Polymerization was carried out at70° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogencontaining 0.09 mol % of hydrogen so as the keep the total pressureconstant. As a result, 98 g of an ethylene-1-butene copolymer wasobtained. The physical properties of the resultant copolymer are shownin Table 1.

TABLE 1 Example Example Example Example Example Example 1 2 3 4 5 6density kg/m³ 929 918 918 920 922 922 MFR g/10 min 1.9 1.03 3.2 5.0 6.816.8 SR — 1.91 2.0 2.04 2.23 2.13 2.20 molecular weight distributionMw/Mn — 10.7 5.2 6.0 5.5 6.4 6.3 Mz/Mw 3.5 3.4 3.0 3.5 3.0 3.0 N_(LCB)1/1000C 0.15 0.14 0.16 0.09 0.18 0.02 N_(SCB) 1/1000C 12.7 17.6 18.317.4 16.0 17.6 [η] 0.99 1.09 1.00 0.96 0.92 0.8 g* — 0.791 0.866 0.8970.877 0.884 0.906 melt complex Pa · sec 469 703 527 420 379 201viscosity Maximum take-up m/min 9 2.1 9.1 18.2 32.1 107.1 velocityimpact strength kJ/m² 241 1121 830 1288 968 596 characteristic second4.93 5.84 1.77 1.71 0.95 0.03 relaxation time flow activation kJ/mol 7474 62 63 58 52 energy Example Example Example Example Example Example 78 9 10 11 12 density kg/m³ 919 920 921 924 921 918 MFR g/10 min 6.4 9.125.07 1.80 5.67 5.26 SR — 2.17 1.97 2.37 1.99 1.87 2.49 molecular weightdistribution Mw/Mn — 9.7 4.6 7.5 6.0 4.7 9.2 Mz/Mw 4.2 2.7 3.9 3.4 3.04.2 N_(LCB) 1/1000C 0.04 0.09 0.06 0.11 0.06 0.06 N_(SCB) 1/1000C 20.617.7 17.7 15.9 16.6 19.8 [η] 0.94 0.91 0.91 1.09 1.0 0.96 g* — 0.9340.888 0.83 0.795 0.831 0.903 melt complex Pa · sec 345 345 394 658 448361 viscosity Maximum take-up m/min 11.7 193.5 7.1 1.8 68.3 2.7 velocityimpact strength kJ/m² 289 653 513 114 133 663 characteristic second 7.430.46 2.49 5.3 2.3 3.2 relaxation time flow activation kJ/mol 109 62 6973 65 70 energy Example Comparative Comparative Comparative 13 Example 1Example 2 Example 3 density kg/m³ 917 924 923 — MFR g/10 min 3.54 2.81.93 1.09 SR — 2.04 2.25 2.0 2.12 molecular weight distribution Mw/Mn —13.3 10.9 12.4 4.5 Mz/Mw 4.4 4.4 4.1 3.8 N_(LCB) 1/1000C 0.05 0.10 0.09— N_(SCB) 1/1000C 21.1 18.6 19.0 13.9 [η] 1.02 1.06 1.11 1.31 g* — 0.9030.843 0.857 0.854 melt complex Pa · sec 385 408 490 919 viscosityMaximum take-up m/min 8.5 2.3 3.4 — velocity impact strength kJ/m² 779128 — — characteristic seconds 7.7 24.44 61.46 31.8 relaxation time flowactivation kJ/mol 70 73 31 65 energy

INDUSTRIAL APPLICABILITY

The present invention is capable of providing an ethylene-α-olefincopolymer excellent in extrusion load, swell ratio and mechanicalstrength, and showing sufficiently short relaxation time of a molecularchain in molten state, and a molded article obtained by extrusionmolding of the copolymer.

1. An ethylene-α-olefin copolymer wherein the copolymer has a monomerunit based on ethylene and a monomer unit based on an α-olefin having 3to 20 carbon atoms, the density (d) is 860 to 950 kg/m³, the melt flowrate (MFR) is 1 to 100 g/10 min, the ratio (Mw/Mn) of the weight averagemolecular weight (Mw) to the number average molecular weight (Mn) is 4to 30, the ratio (Mz/Mw) of the Z average molecular weight (Mz) to theweight average molecular weight (Mw) is 2 to 5, the swell ratio (SR) is1.8 or more, and the characteristic relaxation time (T) obtained bylinear viscoelasticity measurement is 0.01 to 10 seconds.
 2. Theethylene-α-olefin copolymer according to claim 1, wherein the number ofbranches having 5 or more carbon atoms measured by ¹³C-NMR (N_(LCB)) is0.1 or more per 1000 carbon atoms.
 3. A molded article obtained byextrusion molding of the ethylene-α-olefin copolymer according toclaim
 1. 4. A molded article obtained by extrusion molding of theethylene-α-olefin copolymer according to claim 2.